Organosilica nanoparticles and method for making

ABSTRACT

Preparation of Free-Flowing Organosilica Nanoparticles by Forming a solution of an organosilica nanoparticle precursor in a mixed solvent system comprising a first solvent and a second solvent, wherein the first solvent is different from the second solvent, wherein the second solvent has a boiling point which is greater than a boiling point of the first solvent, and wherein the nanoparticle precursor has a greater solubility in the first solvent than in the second solvent; removing at least 50% of the first solvent to form nanoparticles having a mean particle size less than about 25 nanometers dispersed in the solution; adding a coupling agent to the solution to facilitate reacting of the coupling agent with the nanoparticles; and recovering the nanoparticles from the solution, wherein the recovered nanoparticles have the mean particle size of less than about 25 nanometers

REFERENCE TO RELATED APPLICATIONS

This is a continuation-in-part of U.S. patent application Ser. No.12/372,436 filed Feb. 17, 2009, issued Mar. 15, 2011 as U.S. Pat. No.7,907,809, and claims priority to provisional U.S. application61/028,825, filed Feb. 14, 2008.

BACKGROUND OF THE INVENTION

Nanoporous dielectric materials are gaining prominence in the recentyears as they are finding applications in a wide range of fieldsincluding photonics, catalysis, semiconductor processing, biosensors andbioimaging. For example, because of their extremely low refractiveindex, these materials have been considered as a better and a cheaperalternative to Teflon AF in liquid core waveguide applications. Inaddition, the relatively large surface area associated with thesematerials could be efficiently utilized to serve as high densitysubstrates for biomolecule immobilization. With decreasing featuresizes, new materials with ultra low dielectric constant are becoming anincreasingly important requirement in the semiconductor industry atpresent to replace conventional silicon dioxide as the interconnectinsulation material. Suitable materials with ultra low dielectricconstant have to be obtained in order to minimize the RC interconnectdelays.

Various methods have been proposed for the preparation of nanoporousdielectrics. Among the more common are the surfactant templating methodfor ordered porous structures (see, e.g., Y. Lu, R. Ganguli, C. A.Drewien, M. T. Anderson, C. J. Brinker, W. Gong, Y. Guo, H. Soyez, B.Dunn, M. H. Huang, and J. I. Zink, “Continuous formation of supportedcubic and hexagonal mesoporous films by sol-gel dip-coating,” Nature,vol. 389, pp. 364-368, 1997 and C. J. Brinker, Y. Lu, A. Sellinger, andH. Fan, “Evaporation-Induced Self-Assembly: Nanostructures Made Easy,”Advanced Materials, vol. 11, pp. 579-585, 1999) and the porogenextraction method for random pore structures (see, e.g., B. Lee, Y.-H.Park, Y.-T. Hwang, W. Oh, J. Yoon, and M. Ree, “Ultralow-k nanoporousorganosilicate dielectric films imprinted with dendritic spheres,” NatMater, vol. 4, pp. 147-150, 2005 and M. Ree, J. Yoon, and K. Heo,“Imprinting well-controlled closed-nanopores in spin-on polymericdielectric thin films,” Journal of Materials Chemistry, vol. 16, pp.685-697, 2006). In each of these methods, nanoporosity is introduced byforming a nanocomposite film of a thermally labile species (porogen)within an otherwise monolithic matrix material, followed by a hightemperature heating step. Calcination of the porogen leaves behindnanopores in the monolithic matrix material thereby effectivelydecreasing the dielectric constant and refractive index of the film.

The formation of porous films by conventional porogen or surfactanttemplating approaches typically requires highly-controlled slow-curingprocesses to prevent pore collapse. For example, temperature must beclosely controlled during heating, at curing, and then heating tovolatilization. The formed films may suffer from large residual stressesduring the cooling run which may initiate buckling and cracking in thefilms especially when thick films are desired for waveguideapplications. See, e.g., W. Oh, T. J. Shin, M. Ree, M. Y. Jin, and K.Char, “Residual Stress Behavior in Methylsilsesquioxane-Based DielectricThin Films,” Molecular Crystals and Liquid Crystals, vol. 371, pp.397-402, 2001 and W. Oh and M. Ree, “Anisotropic Thermal ExpansionBehavior of Thin Films of Polymethylsilsesquioxane, a Spin-on-GlassDielectric for High-Performance Integrated Circuits,” Langmuir, vol. 20,pp. 6932-6939, 2004. The versatility of these materials coupled withgrowing demand is driving researchers to rethink their fabricationmethodology to achieve them in the most energy efficient andcommercially attractive way.

Another technique of formation of nanoporous films is based on thedeposition of nanoparticles through gas evaporation techniques. See,e.g., S, Nozaki, H. Ono, K. Uchida, H. Morisaki, N. Ito, and M.Yoshimaru, in Interconnect Technology Conference, 2002. Proceedings ofthe IEEE 2002 International, (2002).

Ultra large surface area (201 m²/g) films have previously been reported.See, e.g., T. Miki, K. Nishizawa, K. Suzuki, and K. Kato, “Preparationof nanoporous TiO₂ film with large surface area using aqueous sol withtrehalose,” Materials Letters, vol. 58, pp. 2751-2753, 2004 and M. R.Mohammadi, M. C. Cordero-Cabrera, D. J. Fray, and M. Ghorbani,“Preparation of high surface area titania (TiO₂) films and powders usingparticulate sol-gel route aided by polymeric fugitive agents,” Sensorsand Actuators B: Chemical, vol. 120, pp. 86-95, 2006. The surfaces ofthese ultra large surface area films, however, tend to be relativelyhydrophilic and relatively rough.

Ultra large surface areas have also been reported for porous carbonbased materials. These materials, however, are generally not transparentor smooth.

Surface area values for silica aerogels have been reported to be750-1100 m²/g. See, e.g., B. Zhou, J. Shen, Y. Wu, G. Wu, and X. Ni,“Hydrophobic silica aerogels derived from polyethoxydisiloxane andperfluoroalkylsilane,” Materials Science and Engineering: C, vol. 27,pp. 1291-1294, 2007 and L. L. Aranda, “Silica aerogel,” Potentials,IEEE, vol. 20, pp. 12-15, 2001. Preparation of these aerogels, however,typically requires controlled supercritical drying, etc. Also, silicabased aerogels tend to be relatively hydrophilic which results in amoisture absorption which may, in turn, lead to deterioration of thematerial. Post treatment is thus typically required to render thesematerials hydrophobic to minimize moisture absorption.

The formation of porous films by conventional porogen or surfactanttemplating approaches typically requires highly-controlled slow-curingprocesses to prevent pore collapse. The formed films may suffer fromlarge residual stresses during the cooling run which may initiatebuckling and cracking in the films. See, e.g., W. Oh, T. J. Shin, M.Ree, M. Y. Jin, and K. Char, “Residual Stress Behavior inMethylsilsesquioxane-Based Dielectric Thin Films,” Molecular Crystalsand Liquid Crystals, vol. 371, pp. 397-402, 2001 and W. Oh and M. Ree,“Anisotropic Thermal Expansion Behavior of Thin Films ofPolymethylsilsesquioxane, a Spin-on-Glass Dielectric forHigh-Performance Integrated Circuits,” Langmuir, vol. 20, pp. 6932-6939,2004.

SUMMARY OF THE INVENTION

Among the various aspects of the present invention, therefore, may benoted the provision of nanoporous films; the provision of films havingone or more of the following characteristics: relatively high surfaceareas (at least 600 m²/g; e.g., greater than about 1400 m²/g),relatively low dielectric constant (e.g., less than 2), relatively lowrefractive index (e.g., less than 1.33), and relatively greatthicknesses (e.g., at least 3 micrometers in a single coating); theprovision of processes for the preparation of such films, processeswhich enable the preparation of such films relatively rapidly (e.g., inless than 10 minutes), and the provision of nanoparticles that may bederived from such films.

One aspect of the present invention is a nanoporous film comprisingorganosilica nanoparticles. The organosilica nanoparticles have a meanparticle size of less than about 25 nanometers and a mean pore size ofless than 10 nanometers, and the film has a surface area of at least 500m²/g.

Another aspect of the present invention is a composite comprising ananoporous film on a substrate. The nanoporous film comprisesnanoparticles having a mean particle size of less than about 25nanometers and a mean pore size of less than 10 nanometers, and the filmhas a surface area of at least 500 m²/g.

Another aspect of the present invention is a process for the preparationof a nanoporous film comprising nanoparticles, the process comprisingforming a solution of a nanoparticle precursor in a mixed solvent systemcomprising a first solvent and a second solvent, wherein the firstsolvent is different from the second solvent, wherein the second solventhas a boiling point which is greater than a boiling point of the firstsolvent, and wherein the nanoparticle precursor has a greater solubilityin the first solvent than in the second solvent; removing at least 50%of the first solvent; depositing the solution as a film onto asubstrate; and calcining the deposited film at a temperature of at least200° C. to remove the second solvent from the film to form a nanoporous,nanoparticulate film having a thickness of less than 3 microns, asurface area of at least 500 m²/g, a refractive index of less than 1.33,a dielectric constant of less than 2, and a porosity of at least about50% by volume.

In another aspect the invention is a waveguide comprising at least twospaced-apart opposed surfaces defining a channel therebetween; awaveguide inlet; a waveguide outlet; and a film on each of the twospaced-apart opposed surfaces wherein the film comprises organosilicananoparticles having a mean particle size of less than about 25nanometers and a mean pore size of less than 10 nanometers; wherein thefilm has a surface area of at least 500 m²/g and a porosity of at leastabout 50% by volume; the film has a thickness of less than about 3microns; the film has a dielectric constant of less than 2; and the filmhas a refractive index of less than 1.33.

A further aspect of the invention is a process for the preparation offree-flowing organosilica nanoparticles, the process comprising forminga solution of an organosilica nanoparticle precursor in a mixed solventsystem comprising a first solvent and a second solvent, wherein thefirst solvent is different from the second solvent, wherein the secondsolvent has a boiling point which is greater than a boiling point of thefirst solvent, and wherein the nanoparticle precursor has a greatersolubility in the first solvent than in the second solvent; removing atleast 50% of the first solvent to form nanoparticles having a meanparticle size less than about 25 nanometers dispersed in the solution;adding a coupling agent to the solution to facilitate reacting of thecoupling agent with the nanoparticles; and recovering the nanoparticlesfrom the solution, wherein the recovered nanoparticles have the meanparticle size of less than about 25 nanometers.

Other aspects, objects and features of the invention will be in partapparent and in part pointed out hereinafter.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic illustration of a proposed mechanism for theformation of a nanoparticulate dispersion.

FIG. 2 is a schematic illustration of an optical waveguide.

FIG. 3 is a schematic illustration of an optical waveguide of thepresent invention with hydrophilic and hydrophobic regions.

FIG. 4 is a schematic illustration of a liquid core waveguide of thepresent invention.

FIGS. 5A and 5B are cross-sectional SEM images of a cross-section of ananoparticulate film of the present invention at differentmagnifications, as described in Example 1.

FIGS. 6A and 6B are ellipsometric fitting curves for Psi and Delta,respectively.

FIG. 7A depicts Nitrogen adsorption-desorption isotherms measured forporous organosilicate nanoparticle networks and 7B depicts BET analysisof the isotherms to determine the surface area, as described in Example2.

FIG. 8A is a t-plot analysis of the isotherms show positive Y interceptconfirming the existence of micropores in the samples described inExample 2. The de Boer Statistical Thickness on the x-axis is inangstroms. FIG. 8B shows pore size distributions determined for thesample described in Example 2.

FIGS. 9A and 9B are SEM images of the obtained nanoparticlulate filmsprepared with 14% OH content polymethylsilsesquioxane (Techneglas Corp.GR650F), solution aged 1 day as described in Example 3. Average particlesize ˜10 nm

FIG. 10 is a SEM of the nanoparticulate film prepared with 2% OH contentpolymethylsilsesquioxane (Gelest, SST-3M02) as described in Example 3.The average particle size is about 40 nm.

FIGS. 11A, 11B, and 11C are TEM images of the organosilicatenanoparticle dispersions prepared as described in Example 4; (a) and (b)prepared with 14% OH content polymethylsilsesquioxane, and (c) Preparedwith 2% OH content polymethylsilsesquioxane. Scale bar for (b) is 200 nmand the scale bar for (c) is 500 nm.

FIG. 12 is an ATR-FTIR spectra of the Hexane treated and untreated gelsaged the same time as described in Example 5.

FIG. 13 is an ATR-FTIR spectra of the microwave treated gel as describedin Example 5.

FIG. 14 is a TEM image of the particles obtained from hexane treated gelas described in Example 5. Scale bar is 100 nm.

FIGS. 15A and 15B are TEM images of the microtomed samples of theprocessed gel: A, completely formed nanorod structures, and B,intermediate structure (scale bar=200 nm) as described in Example 6.

FIG. 16 is a schematic of the conjugation protocol of NPO and asdescribed in Example 9.

FIG. 17 are photographs depicting immunofluorescences of chick heartstaining using an antibody (against laminin-1) conjugate with Rhodaminedoped nano-particles as described in Example 9.

FIG. 18 is a time dependent decay in fluorescence of a tissue stainedwith an antibody conjugated with doped Rhodamine nanoparticles asdescribed in Example 9.

FIG. 19 is a TEM image (scale bar=20 nm) of the rhodamine 6G Doped NPOparticles derived fom the film as described in Example 9.

FIG. 20 is a schematic depiction of a mask design for patterningchannels on silicon substrates (FIG. 20A) and glass substrates (FIG.20B) as described in Example 11.

FIG. 21 is a fabrication flow chart for the liquid core waveguide asdescribed in Example 11.

FIG. 22 is a photograph of the experimental setup for losscharacterization of the prototype liquid core waveguide as described inExample 11.

FIG. 23 is a photograph, illustrating the waveguiding effect using aprototype liquid core waveguide as described in Example 11.

FIG. 24 is a graph showing the loss characteristics for the prototypeliquid core waveguide as described in Example 11.

FIGS. 25A-25F are a series of SEM micrographs of the nanoparticulateorganosilicate films obtained as described in Example 12.

FIGS. 26A-26B are a series of SEM micrographs of the nanoparticulateorganosilicate films obtained as described in Example 12.

FIGS. 27A-27E are a series of graphs of thickness, refractive index anddielectric constant for films prepared as described in Example 12.

FIGS. 28A-28E are a series of graphs of thickness, refractive index anddielectric constant for films prepared as described in Example 12.

FIGS. 29A and 29B are photographs of circularly patternedphoton-emitting films of Example 13.

FIG. 30 is TEM image of nanorods prepared in accordance with Example 14.

FIGS. 31 and 32 are fluorescence intensity plots of Example 15.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with one aspect of the present invention, nanoporous filmshaving a relatively high surface area may be prepared. These films arecrack-resistant and may additionally be relatively hydrophobic, exhibitan ultra-low refractive index, and/or exhibit a low dielectric constant.Because the films are nanoparticulate, nanoparticles possessing uniqueproperties may also be derived from such films. Consequently, films ofthe present invention potentially have a wide range of uses including,for example, microbiological applications, the microelectronicsindustry, and photonics.

Nanoporous Films

In general and as described in more detail below, nanoporous films ofthe present invention are prepared by steps including but not limited toforming a solution containing a nanoparticle precursor in a solventsystem, subjecting the solution to a treatment which causesnanoparticles to form from the nanoparticle precursor, depositing thesolution onto a substrate, and curing the deposited solution to form afilm. The invention employs a liquid dispersion of a nanoparticleprecursor from which discrete nanoparticles are formed and a porogen ina solvent system. Other optional additives include, for example, activepharmaceutical agents, proteins, peptides, nucleic acids, antibodies andother biologicals, metals or fluorescent dyes to tailor the films ornanoparticles derived therefrom for use in microelectronic or bioprobeapplications.

In general, the nanoparticle precursor may be any of a range of organicand inorganic solids In one embodiment, for example, the nanoparticleprecursor comprises an organo metal (or semi-metal) such as aluminum,titanium, or silicon. Exemplary organotitanium compositions includetitanium(IV) isopropoxide, titanium tetraisopropoxide andmethyltitaniumtriisopropoxide. Examplary organoaluminum compositionsinclude aluminum n-butoxide, aluminum d-butoxide, aluminumdiisopropoxide ethyl acetoacetate, aluminum ethoxide, aluminum ethoxyethoxy ethoxide, and aluminum isopropoxide.

In one preferred embodiment, the nanoparticle precursor is anorganosilica material containing any of a range of materials includingsilicon, carbon, oxygen and hydrogen atoms known to those of ordinaryskill. Exemplary organosilica materials include, but are not limited to,silsesquioxanes (RSia_(1.5) where R is an organic substituent),partially condensed halosilanes or alkoxysilanes such as partiallycondensed by controlled hydrolysis of tetraethoxysilane, organicallymodified silicates having the composition RSiO₃ or R₂SiO₂ wherein R isan organic substituent, and partially condensed orthosilicates havingSi(OR)₄ as the monomer unit. Exemplary silsesquioxanes include alkylsilsesquioxanes such as methyl silsesquioxane, polymethylsilsesquioxane(“PMSSQ”), ethyl silsesquioxane, propyl silsesquioxane, butylsilsesquioxane and the like; aryl silsesquioxanes such as phenylsilsesquioxane and tolyl silsesquioxane; alkyl/aryl silsesquioxanemixtures such as a mixture of methyl silsesquioxane and phenylsilsesquioxane; and mixtures of alkyl silsesquioxanes such as methylsilsesquioxane and ethyl silsesquioxane. PMSSQ, for example, isavailable from Techneglas of Perrysburg, Ohio under the tradedesignation GR650F, which is in the form of colorless flakes.

In one embodiment, it is generally preferred that the organosilicamaterial be a silsesquioxane, and more preferably hydridosilsesquioxane, methyl silsesquioxane, ethyl silsesquioxane, propylsilsesquioxane, iso-butyl silsesquioxane, tert-butyl silsesquioxane,phenyl silsesquioxane or mixtures thereof. For example, thesilsesquioxanes may be present as a mixture including hydridosilsesquioxanes and alkyl, aryl or alkyl/aryl silsesquioxanes. Otherexemplary silsesquioxanes include combinations of alkyl or arylsilsesquioxanes with tetra(C₁-C₆)alkylorthosilicates such astetraethylorthosilicate, or copolymers or composites thereof. In oneembodiment, the silsesquioxane is hydrogen silsesquioxane or methylsilsesquioxane and preferably methylsilsesquioxane. In one preferredembodiment, the organosilica is polymethylsilsesquioxane. In oneparticularly preferred embodiment, the organosilica ispolymethylsilsesquioxane having a hydroxy content of 0.5 to 20%,preferably about 2-14%.

Typically, the silsesquioxane(s) or other organosilica materialsincluded in the liquid disperson have a number average molecular weight,M_(n), of about 5,000 to about 20,000 daltons. For example, in oneembodiment, the silsesquioxane(s) or other organosilica materialsincluded in the liquid disperson have a molecular weight, M_(n), ofabout 5,000 to about 15,000 daltons. By way of further example, in oneembodiment, the organosilica material included in the liquid dispersonis a silsesquioxane or mixture thereof having a molecular weight, M_(n),of about 6,000 to about 9,000 daltons.

The organosilica (alone, or in combination with another nanoparticleprecursor) is dispersed in a solvent system. In one embodiment, thesolvent system comprises a mixture of miscible, but different solvents,referred to herein as a first solvent and a second solvent. The firstsolvent is a “good” solvent in the sense that the nanoparticle precursoris relatively more soluble in this first solvent than in the secondsolvent. In general, a range of solvents or mixtures of solvents may beemployed. In one embodiment, the first solvent may be selected fromalcohols, ketones, amides, esters, or combinations thereof. For example,one of the first solvents may be selected from relatively low boilingpoint solvents such as ethanol, 1-methoxy-2-propanol (propylene glycolmonomethyl ether), tetrahydrofuran, acetone, 1,4-dioxane, 1,3-dioxolane,ethyl acetate, and methyl ethyl ketone. In other embodiments, one of thesolvents may be selected from relatively high boiling point solventssuch as dimethylformamide, dimethylacetamide, N-methylpyrrolidone,ethylene carbonate, propylene carbonate, glycerol and derivatives,naphthalene and substituted versions, acetic acid anyhydride, propionicacid and propionic acid anhydride, dimethyl sulfone, benzophenone,diphenyl sulfone, phenol, m-cresol, dimethyl sulfoxide, diphenyl ether,terphenyl, and the like.

In one embodiment, preferred solvents for use as the first solventinclude propylene glycol propyl ether (PGPE), 3-heptanol,2-methyl-1-pentanol, 5-methyl-2-hexanol, 3-hexanol, 2-heptano,2-hexanol, 2,3-dimethyl-3-pentanol, propylene glycol methyl etheracetate (PGMEA), ethylene glycol n-butyl ether, propylene glycol n-butylether (PGBE), 1-butoxy-2-propanol, 2-methyl-3-pentanol, 2-methoxyethylacetate, 2-butoxyethanol, 2-ethoxyethyl acetoacetate, 1-pentanol, andpropylene glycol methyl ether. One particularly preferred first solventfor use in the solvent system is propylene glycol methyl ether acetate.Still further exemplary solvents include lactates, pyruvates, and diols.The solvents enumerated above may be used alone or in combination of twoor more solvents; for example, the solvent may comprise one or moresolvents with relatively low boiling points, i.e., boiling points below160° C., one or more solvents with relatively high boiling points, i.e.,boiling points above 160° C., or a mixture of one or more solvents withrelatively low boiling points and relatively high boiling points.

To aid in the formation of the nanoparticulate nanoporous film, theliquid dispersion comprises a composition which is used to generatepores, sometimes referred to as a porogen. In many preferredembodiments, the second solvent (bad solvent) functions as the porogen,and is the same component as the second solvent (bad solvent). Ingeneral, the porogen has a molecular weight less than 1,500 Daltons. Forexample, the porogen may be a polymer having a molecular weight, M_(n),of less than 1500 Daltons. In one embodiment, the porogen is a polymerhaving a molecular weight, M_(n), of less than 1000. In one preferredembodiment, the porogen is a polymer having a molecular weight, M_(n),of about 400 to about 700 Daltons. However, in the two-step process ofthe invention where the porogen is not incorporated until afterformation of the nanoparticles, the molecular weight of the porogen isnot important (may be as high as, e.g., 20,000), provided it decomposesat elevated temperatures.

In one preferred embodiment as noted above, the porogen may beconsidered to be a “bad” or “poor” solvent for the nanoparticleprecursor. In this embodiment, and for ease of discussion, the porogenis referred to herein as the “second” or “bad” or “poor” solvent and theother solvent(s) of the solvent system in which the organosilicamaterial (or other nanoparticle precursor(s)) has significantly greatersolubility is referred to herein as the “first” or “good” solvent. Inthis embodiment, the first solvent can be selectively removed from theliquid dispersion by evaporation relative to the second solvent. As aresult, when the solvent system is a mixed solvent system, initiallycontaining both first and second solvents, the organosilica moleculesare in a relatively uncoiled, i.e., an extended state. In a “good”solvent, the chains are extended and in a “poor” solvent on the otherhand, the chain molecules assume a highly coiled (globule) form. See,e.g., Claudine Williams, Francoise Brochard, Harry. L Frisch, Ann. Rev.Phys. Chem. 32, 51 (1981), incorporated herein by reference. When,however, the first solvent is selectively removed from the mixed solventsystem of the liquid dispersion, the organosilica molecules (or othernanoparticle precursor(s)) are induced into an increasingly coiled orcompacted state to minimize their enthalpic interactions with the secondsolvent molecules which increase in relative concentration as the firstsolvent is selectively removed from the system. The dynamic equilibriumis thus shifted towards the formation of small nuclei by the selectiveremoval of the first solvent. See, e.g., Hiroshi Yabu, Takeshi Higuchi,Kuniharu Ijiro, Masatsugu Shimomura, CHAOS 15, 047505, (2005),incorporated herein by reference.

In one embodiment, any of the aforementioned solvents having a boilingpoint greater than about 200° C. is chosen as the porogen (or “second”solvent). In another embodiment, the porogen is a decomposable polymer,many types of which are well known in the art. See, e.g., the examplesof decomposable polymers identified in U.S. Pat. No. 5,895,263, theentire disclosure of which is incorporated herein by reference. In onepreferred embodiment, the porogen is a polyol. For example, the polyolmay be a monomeric polyol such as pentaerythritol, ethylene glycol orglycerin. Alternatively, and more preferably, the polyol is a polymericpolyol. Preferred polymeric polyols include polyester and polyetherpolyols. In one embodiment, the porogen is a linear or branched polymerselected from the group consisting of polyesters, polylactides,polystyrenes substituted polystyrenes, poly-alpha methylstyrene,substituted poly-alpha methyl polystyrenes, aliphatic polyolefins,polynorbornenes, polyacrylates, polymethacrylates, and polyethers. Notall porogens function as a second solvent. So there are situations wherethe porogen and the second solvent are the same element; and there aresituations where the porogen and the second solvent are not the sameelement. Components which have been shown to function as both a porogenand a second solvent include PPG (MW-424), PEG (MW-300), PEG (MW-400)(polyethylene glycol). Exemplary polyethers include polyethylene oxide,poly(propylene glycol) and polytetrahydrofuran. Poly(propylene glycol),also known as polypropylene oxide, is particularly preferred.

In one embodiment, the liquid dispersion contains a substantial amountof the porogen relative to the organosilica material (and/or othernanoparticle precursor) and the first solvent. For example, the liquiddispersion will typically contain between about 30:70 and about 70:30parts by weight of the porogen and the organosilica (and/or othernanoparticle precursor), respectively. In one preferred embodiment, theliquid dispersion will contain between about 40:60 and about 60:40 partsby weight of the porogen and the organosilica (and/or other nanoparticleprecursor), respectively. By way of further example, in one embodimentthe liquid dispersion contains between about 45:55 and about 55:45 partsby weight of the porogen and the organosilica (and/or other nanoparticleprecursor), respectively. Similarly, the liquid dispersion willtypically contain between about 10:90 and about 60:40 parts by weight ofthe porogen and first solvent, respectively. In one preferredembodiment, the liquid dispersion contains between about 20:80 and about50:50 parts by weight of the porogen and first solvent, respectively.Viewed in combination, therefore, in one embodiment the liquiddispersion may contain about 25:25:50 parts by weight of theorganosilica (and/or other nanoparticle precursor), the porogen and thefirst solvent, respectively.

In addition to the nanoparticle precursor, the porogen, and the solventsystem, the liquid dispersion may optionally contain various additivesto tailor the film (or particles to be derived therefrom) for particularend-uses. For example, the liquid dispersion may include fluorescentdyes to be incorporated into the film (or particles to be derivedtherefrom), active pharmaceutical agents, metal nanoparticles, nucleicacids, proteins, and peptides.

The liquid dispersions may be formed by merely combining thenanoparticle precursor, the porogen, the first solvent, and any otherdesired additives. In a preferred embodiment, however, the liquiddispersion is formed by combining two clear solutions, e.g., solution“A” and solution “B” wherein solution “A” contains the porogen and thefirst solvent in approximately equal parts by weight of each, andsolution “B” contains the organosilica and the first solvent inapproximately equal parts by weight. Regardless of the order of mixing,in one preferred embodiment the liquid dispersion initially containsabout 10:40:50 to about 40:10:50 parts by weight of the organosilica,porogen, and first solvent, respectively. In addition, solution “A” or“B” or each may be sonicated to improve the rate of dissolution. What isformed is an overall solution of the precursor, porogen, and othercomponents. This solution is then treated to cause the formation ofnanoparticles as described more fully below.

After combining, the concentration of the first solvent in the resultingliquid dispersion is reduced by heating and/or evaporation. The liquiddispersion may be heated using microwaves or by conventional, e.g.,thermal, heating apparatus such as an oven or hotplate. Regardless ofthe means employed, the liquid dispersion may be heated to reduce theconcentration of the first solvent to, for example, 9:36:45 parts byweight of the nanoparticle precursor, first solvent, and second solvent,respectively. Selectival removal of the second solvent may also becarried out (or supplemented by) vacuum evaporation which typicallyoccurs, at least to some extent, when the precursor solution isdeposited on a substrate either by spin coating or dip coating. In oneembodiment, therefore, the first solvent is selectively removed byheating the liquid dispersion. In another, the first solvent isselectively removed by reducing the atmospheric pressure over the liquiddispersion. In yet another, the liquid dispersion is heated and theatmospheric pressure is reduced to selectively remove the first solvent.As noted, selective removal of the first solvent is the preferred methodof the invention; but there are circumstances and component combinationsin which nanoparticle formation may also be observed by simply mixingthe two solutions followed by film deposition (skipping the evaporationstep). Advantageously, as the concentration of the first solventdecreases, the extent of formation of nanoparticles increases.

In a further alternative embodiment, the solvent system consistsentirely of a solvent which functions as a porogen, i.e., it consistsentirely of a second solvent in which the nanoparticle precursorparticles are relatively insoluble. An example of this approach is PMSSQprecursor nanoparticles in PPG (M_(n) 424) as the second solvent whichalso functions as porogen. This is the case when the first solvent iscompletely evaporated from the system as it happens during filmdeposition through spin coating or dip coating techniques.

Without being bound to a particular theory, FIG. 1 schematicallyillustrates the inventors' expected formation mechanism for thenanoparticles employed in the films of the invention. At the outset, asshown in the leftmost segment 1, the liquid dispersion is at e.g., 27°C. and contains random coils of the precursor such as organosilica,e.g., PMSSQ. As time passes, and the liquid dispersion is heated toe.g., 75° C. to evaporate the first solvent, the relative concentrationof the second solvent is enriched which forces the precursor chains toassume a globule shape, intramolecular crosslinking is initiated asshown in segment 2 as the first solvent evaporates. This crosslinkingcontinues during the evaporation step through segments 2, 3, and 4,still at 75° C. And as the solution is cooled to, e.g., 27° C. as shownin segment 5, eventually resulting in a sol-gel type of network.

In carrying out one embodiment of the invention to form thenanoparticles, therefore, the solution containing the precursur, firstsolvent, porogen, and other components is heated to a temperature atwhich the first solvent evaporates. This temperature is selecteddepending on the particular solvent system, and is, for example, atleast about 0° C., for example, between about 0 and about 75° C. Thesolution is then held at that temperature for a period of time toachieve the desired evaporation, for example, up to about 30 minutes. Inone preferred embodiment, where the precursor ispolymethylsilsesquioxane (PMSSQ), the porogen is poly(propyleneglycol)(M_(n) 424), and the first solvent is propylene glycol methylether acetate (PGMEA), the liquid dispersion is heated to about 73° C.to remove 2-40% of the PGMEA initially present in the liquid dispersion.So in the preferred embodiment used herein for illustration, as timepasses, and the liquid dispersion is heated to evaporate the PMGEA firstsolvent, the relative concentration of the PPG molecules get enrichedforcing the PMSSQ chains to assume a compact globule shape to minimizethe enthalpic interactions of the relatively hydrophobic PMSSQ chainswith the relatively hydrophilic PPG chains. The precursor PMSSQmolecules further undergo intramolecular crosslinking as time passes.After cooling, the dispersion continues to increase in viscosity andeventually gels with time, e.g., in a period of 0.5-10 days at roomtemperature.

In general, the film-forming step of the invention is performed bydepositing the liquid dispersion onto a substrate to form a film whichcoats the substrate. Exemplary substrates include, but are not limitedto, ceramics, glass, metal, polymers, or even semiconductor materialssuch as single crystal silicon, polycrystalline silicon, amorphoussilicon, silicon dioxide, silicon nitride, compound semiconductors suchas gallium arsenide, and combinations thereof. The liquid dispersion maybe applied onto the substrate via a variety of methods including, butnot limited to, dipping, rolling, brushing, spraying, or spin coating.As a general proposition, the thickness of the deposited film at thispoint is from about 10 (e.g., 12) to several tens of nanometers, e.g.,50 nanometers, to several micrometers, e.g., 2 micrometers, 3micrometers, or greater than 3 micrometers in a single deposition.During this deposition operation and/or in a subsequent lowertemperature operation thereafter, all of the remaining proportion of thefirst solvent evaporates.

To obtain the desired nanoparticulate porous film, after deposition ofthe dispersion, the coated substrate is typically calcined at atemperature of at least about 200° C. to remove the porogen from thecoating. In certain embodiments, the calcining step is conducted at twoor more temperatures rather than as a controlled slow ramp or soak. Thefirst temperature, typically 70° C., is to remove any first solventremaining in the dispersion and to further crosslink the organosilica.In many embodiments, however, most or all of the first solvent isremoved from the dispersion prior to film-forming and residual firstsolvent is removed during the spin-coating or other film-formingprocess. Advantageously, therefore, in these embodiments there is noneed for a separate temperature hold at e.g. 70° C. or other allowanceduring the calcining operation for removal of the first solvent.

In one preferred embodiment, the coated substrate is calcined at atemperature of at least 300° C. In another preferred embodiment, thecoated substrate is calcined at a temperature of at least 400° C. Forexample, the coated substrate is calcined at a temperature in the rangeof about 450° C. to about 600° C. Specific temperature and timedurations for calcination vary depending upon the components of thedispersion, the substrate, and the desired pore volume. The calcinationtemperature of at least 200° C., 300° C., 400° C., e.g., about 450° C.to about 600° C. is to remove the porogen and to substantially, but notnecessarily completely, crosslink the material. The calcining step istypically conducted for a time of about 30 minutes or less, preferablyabout 15 minutes or less, and more preferably about 6 minutes or less. Aslow temperature ramp rate results in densification and loss ofporosity; so it is preferred to expose the films instantaneously to thecalcination temperature, for example using a pre-heated hot plate. Inthis way the films at a temperature and in an environment of, e.g., lessthan 100° C. are exposed instantaneously (e.g., in less than about 10seconds) to the calcining temperature of at least 200° C., 300° C., 400°C., e.g., about 450° C. to about 600° C.

During calcination, the porogen such as PPG essentially decomposes andthe expanding gases offer a great increase in the translational entropyto the PMSSQ particles. The nanoparticles suspended in the gaseousdecomposition products of PPG are in a Brownian state of motion with anaverage kinetic energy of each particle being 3/2kT. With the existenceof a temperature gradient between the substrate and the ambient, thenanoparticles experience a net diffusion outward, away from thesubstrate The increased internal energy of each individual nanoparticleresults in their intra-particle crosslinking, while the random movementand collision between the particles results in their inter-particlecrosslinking finally driving the system to equilibrium and resulting ina porous nanoparticulate film. For this reason, the porosity of thefilms is greatly dependent on the curing/calcination temperature.Accordingly, the calcination is specifically performed at a temperaturebeyond the decomposition temperature of the porogen, e.g., polymer suchas PPG. An increase in system entropy above the decompositiontemperature of the porogen provides a high degree of mobility to thenanoparticles. Calcination may be carried out via thermal methods suchas a hot plate, oven, furnace or the like. For thermal methods, thecuring of the coated substrate may be conducted under controlledconditions such as atmospheric pressure using nitrogen, inert gas, air,or other N₂/O₂ mixtures, vacuum, or reduced pressure having controlledoxygen concentration.

The system employed in the invention therefore consists of functionalnanoparticles that can be thermally initiated to undergo interparticleas well as intraparticle crosslinking, dispersed in a thermally labilepolymer layer. The behavior of this system depends on the calciningtemperature, the temperature ramp rate, and the surface energy of thesubstrate it is deposited on. In accordance with this invention, thinfilms of PMSSQ nanoparticles dispersed in PPG result in the formation ofporous films when they are deposited on, e.g., hydrogen-passivatedsilicon substrates and subjected to instant temperature gradients abovethe decomposition temperature of PPG. In contrast, at temperatures lowerthan the decomposition temperature of PPG and therefore lower thantemperatures employed in this invention, PPG chains play an active rolein maximizing the system entropy. Segregation of the nanoparticles takesplace at these temperatures whereby the nanoparticles lose theirtranslational entropy. This loss of translational entropy of thenanoparticles is however offset by the gain in the conformationalentropy of PPG chains as there is a far greater entropic penalty imposedin stretching the PPG chains around the nanoparticles to maintain auniform distribution. This results in the eventual expulsion of PPG fromthe film resulting in a dense film void of any pores. As a corollary,films subjected to slow temperature ramp rates to temperatures wellabove the decomposition temperature of PPG essentially result innon-porous films. Finally, these films when deposited on high surfaceenergy substrates followed by the high temperature treatment stepresults in dense, non-porous films. For example, films deposited onfreshly piranha cleaned glass substrates and subjected to theinstantaneous high temperature curing/calcination step resulted in theformation of dense films void of any porosity. The enthalpicinteractions between the nanoparticles and the substrate outweigh theirtranslational entropy gain resulting in the segregation of thenanoparticles to the substrate and the eventual formation of non-porousdense films. Accordingly, to avoid the formation of dense filmsapproaching non-porous, the present invention in a preferred embodimentemploys a combination of a relatively high temperature, high temperatureramp rate, and lower surface energy substrate. A preferred surfaceenergy of the substrate lies between 32 mJ/cm² and 48 mJ/cm². Filmsdeposited on lower surface energy substrates (e.g., 28 mJ/cm²) result indewetting and formation of a discontinuous film.

Calcination of the coated substrate according to this inventiontherefore yields a composite of a nanoporous and nanoparticulate film ona substrate. Depending primarily upon the coating technique and thequantity and viscosity of the liquid dispersion deposited onto thesubstrate, the nanoporous film may have a thickness ranging from about10 (e.g., 12) to several tens of nanometers, e.g., 50 nanometers, toseveral micrometers, e.g., 2 micrometers, 3 micrometers, or greater than3 micrometers in a single deposition. Layers having a thicknesssignificantly greater than 3 micrometers could, for example, be obtainedby repeating the operation, i.e., depositing the liquid dispersion ontoa substrate to form a coated substrate, calcining the coated substrateto obtain a composite of a nanoporous film on a substrate, and repeatingthis sequence of steps at least once to increase the thickness of thenanoporous film with each successive series of steps.

In one embodiment, these methods are used to prepare nanoporous filmshaving pores having a mean size ranging from less than 1 nanometer to 15nanometers, for example of less than 10 nm. Typically, the pores have amean size of on the order of 4 nm with size distribution ranging from0.8 to 10 nanometers. In addition, the film will have a high degree ofporosity, e.g., at least 20% of the total volume of the film is porevolume. In one embodiment, the porosity is greater. For example, in oneembodiment, the film has a porosity of at least 50%. By way of furtherexample, in one embodiment, the film has a porosity of at least 70% byvolume. All porosity values herein are by volume unless indicatedotherwise. Pore sizes in these ranges are well below the wavelength ofvisible light making these films smooth and transparent in the visiblerange.

In general, as the porosity of the film increases, the surface area ofthe film increases and the refractive index of the film decreases, alongwith a decrease in mechanical strength. In accordance with one aspect ofthe present invention, nanoporous films having a refractive index ofless than 1.33 such as less than 1.2 are obtained (as measured at awavelength of 633 nm). In one preferred embodiment, the nanoporous filmhas a refractive index of less than 1.15. In another preferredembodiment, the nanoporous film has a refractive index of less than1.10. Ultra low refractive index nanoporous films, i.e., films havingrefractive indices of 1.048-1.19 are thus obtainable in accordance withthe present invention. Moreover, crack-free, relatively thick (at least2 micrometers), ultra low refractive index nanoporous films may beobtained in a single coating. Relatedly, nanoporous films of the presentinvention may be characterized by a surface area of at least 600 m²/g.In one embodiment, the nanoporous films have a surface area of at least1200 m²/g, and even greater than 1400 m²/g.

The nanoporous films comprise nanoparticles, preferably organosilicatenanoparticles, with diameter sizes that are readily tunable by selectionof liquid dispersion components and process conditions. The percentageOH content of the nanoparticle precursor as well as its molecular weightdetermines the nanoparticle size. For example, nanoparticles havingdiameters of as little as 2 nanometers or as great as 30 nanometers maybe readily obtained. In addition, the nanoparticles may have arelatively narrow size distribution. For example, 30% by weight of thenanoparticles in the film may have a diameter in the range of 2-5nanometers. By way of further example, 70% by weight of thenanoparticles in the film may have a diameter in the range of 6-10nanometers. “Diameter” here loosely refers to the largest dimensionacross a particle because the particles are not strictly spherical.

As previously noted, one aspect of the present invention is nanoporous,nanoparticulate films having relatively low dielectric constants. Ingeneral, nanoporous, nanoparticulate films having a dielectric constantof less than 2 may be readily produced. Depending upon the application,nanoporous films having even lower dielectric constants may be desired.Thus, one aspect of the present invention is the preparation ofnanoporous films having a dielectric constant of less than 1.8. Forexample, for some applications, it may be desired that the nanoporous,nanoparticulate film have a dielectric constant of less than 1.5. Forother applications, it may be desired that the film have an even lowerdielectric constant, e.g., 1.4. The nanoporous, nanoparticulate films ofthe present invention can be achieve these objectives.

In addition to the organosilica nanoparticles, the nanoporous,nanoparticulate film may include other components to tailor the film (ornanoparticles to be derived therefrom) for a microelectronic,microbiologic or other application. For example, the nanoporous,nanoparticulate film may include a mixture of dielectric materials suchas two or more organosilica dielectric materials or a mixture of anorganosilica dielectric matrix material with one or more otherdielectric matrix materials (e.g., an inorganic material such ascarbides, oxides, nitrides or oxyfluorides of silicon, boron, oraluminum; or non-organosilica organic materials such asbenzocyclobutenes, poly(aryl esters), poly(ether ketones),polycarbonates, polyimides, fluorinated polyimides, polynorbornenes,poly(arylene ethers), polyaromatic hydrocarbons, such aspolynaphthalene, polyquinoxalines, poly(perfluorinated hydrocarbons)such as poly(tetrafluoroethylene), and polybenzoxazoles. In general, itis preferred that when a mixture of an organosilica material and atleast one other dielectric matrix material is used, the organosilicamaterial is present as a predominant component. It is further preferredthat the organosilica dielectric matrix material in such admixtures ismethyl silsesquioxane, phenyl silsesquioxane or mixtures thereof.

Instead of, or in addition to, a plurality of dielectric materials, thenanoporous, nanoparticulate film may also contain a metal, a fluorescentcomposition, or other functional moiety (e.g., active pharmaceuticalagents, proteins, peptides, nucleic acids, antibodies, and the like) totailor the nanoporous film (or nanoparticles derived therefrom) forvarious end uses. Exemplary metals include gold, silver, platinum,palladium, iron and cobalt. Similarly, the fluorescent composition maybe a fluorescent dye. The fluorescent dye may be short-lived orlong-lived in fluorescent emission and further characterized by Stokesshift, and quantum yield. Fluorescein isothiocyanate represents acommonly used reactive fluorescent marker that is short-lived inemission, possesses a relatively narrow Stokes shift, and has arelatively high quantum yield. Rhodamine is another commonly usedfluorescent dye, which emits at a longer wavelength than fluorescein.Lanthanide metal chelates represent a class of fluorescent compoundswhich possess a relatively large Stokes shift and are long-lived influorescent emission. This class of fluorescent molecules generallyrequires another strongly absorbing molecule to transfer the lightenergy to induce the strong fluorescence. Examples of lanthanide metalsare terbium and europium which are commonly chelated by a polydentatechelate. Other examples of fluorescent compounds include napthalenes,pyrenes, coumarin derivatives, pyridyloxazole derivatives, and rutheniumcomplexes. As previously noted, these components may be convenientlyincorporated into the nanoporous film by adding them to the liquiddispersion from which the nanoporous film is derived.

Depending upon the application, the nanoporous, nanoparticulate film maybe relatively more hydrophilic, relatively more hydrophobic orintermediate of the two. In general, the degree of hydrophilicity may bedetermined by the contact angle of a droplet of water with contactangles of at least 90° generally being regarded as hydrophobic andcontact angles of less than 90° generally being regarded as hydrophilic.The degree of hydrophilicity may be controlled, at least in partinitially, by selection of organosilica materials. In general, thosewith greater hydroxyl content and less alkyl substitution tend to bemore hydrophilic and those with less hydroxyl content and more alkylsubstitution tend to be more hydrophobic. In addition, the nanoporous,nanoparticulate films may be rendered more hydrophilic by surfaceoxidation to introduce silanol groups. One such approach is by exposureto oxygen plasma. In one embodiment, therefore, a droplet of water onthe nanoporous film will have a contact angle of less than 90°. Forexample, in one embodiment the contact angle may be less than 60°. In afurther embodiment, the contact angle may be less than 30°. In a stillfurther embodiment, the contact angle may be less than 20° such as, forexample, 10°. A significant advantage in comparison to many prior artfilms is that the films of the invention can be made to be inherentlyhydrophobic. In many applications this can be critical to avoidinguptake of water during processing, handling, and storage. Moreover,hydrophilicity can be easily imparted to these hydrophobic films shortlyprior to their incorporation into, for example, biological applicationswhere hydrophilicity may be required.

Nanoparticles

In one aspect the present invention is directed to nanoparticles havingdiameters of as little as 2 nanometers or as great as 30 nanometers. Theparticles may be in form of nanorods, e.g., nanoparticles having alength to diameter (aspect ratio) of at least 2:1, or as particleshaving an aspect ratio in which the greatest dimension is less thantwice the smallest dimension, such as roughly sphere-like shapes.Regardless of aspect ratio, the nanoparticles may have a relativelynarrow size distribution. For example, 30% by weight of thenanoparticles may have a diameter in the range of 2-5 nanometers. By wayof further example, 70% by weight of the nanoparticles may have adiameter in the range of 6-10 nanometers.

The nanoparticles may be derived from the nanoporous, nanoparticulatefilms of the present invention, by mechanically or acousticallyfracturing the nanoporous, nanoparticulate film, for example, byscraping or sonication, or scraping followed by sonication in a suitablesolvent.

Alternatively, nanoparticles may be obtained directly from the solutionphase by precipitation, e.g., by addition of a solvent mixture of waterand ethanol in the presence of suitable surfactants. Alternatively, thenanoparticles may be obtained by spray pyrolysis as described, forexample, in U.S. Pat. No. 7,276,224. When organosilanes are used as thenanoparticle precursor, particle size may be controlled, in part, bytreating the organosilane with a silane coupling agent, for example,trimethyl chlorosilane (TMCS), octadecyl trichlorosilane (OTS) or thelike, which will reduce the degree of interparticle crosslinking.

In addition to obtaining hydrophobic nanoparticles directly from thenanoporous, nanoparticulate films through scraping, hydrophobicnanoparticles can be directly precipitated from the nanoparticulateprecursor solution in bulk quantities. Nanoparticulate precursorsolution is prepared as described above. The wt % of porogen such as PPGis kept at 50% with respect to the precursor such as PMSSQ, and, forexample, PMA is chosen as the good solvent. In one embodiment, theprecursor solution is heated at 70° C. for 20 minutes under stirring toallow the formed PMSSQ nanoparticles to crosslink.

In carrying out this direct formation method, the precursor solution(e.g., 1 mL) following the evaporation step is diluted (e.g., to 10 mlin ethanaol). The silane coupling agent (e.g., 150 microliter TMCS) isadded dropwise to this solution. Generally speaking, the preferredsilanes are alkoxy silanes and chlorosilanes. These moleculesfunctionalize the nanoparticle surfaces. For example, if the purpose ofthe nanoparticles is to impart hydrophobic character to the finalcomposite, then silane coupling agents with terminal hydrophobicfunctionality, e.g., with methyl or fluorine terminated groups, isappropriate. When the nanoparticles are for use in composite systems,these molecules are selected to be compatible with the matrix materialto which the nanoparticles will be added. For example, for preparingepoxy-based nanocomposite systems, the nanoparticle surfaces arefunctionalized via the silane coupling agent, with appropriate agents(e.g., amine terminated surfaces, glycidyl terminated functionality);for acrylate systems (acrylate terminated groups etc.). For sol-gelbased systems, these nanoparticles are usually compatible after anysurface modification due to the presence of an unreacted fraction of OHfunctionality. Suitable silane coupling agents are well understood inthe art. For example, the publication Gelest, Silane Coupling Agents:Connecting Across Boundaries (2006), which is included in thisapplication's information disclosure statement, and incorporated hereinby reference, includes a number of suitable alkoxy silane couplingagents, depending on the desired functionality and compatibility. In oneembodiment, silane coupling agent has the following formula:

(RO)₃—Si—RT

where R is an alkyl and RT is a functional group.

Some agents of interest have chloro silane (Si—Cl) groups with specificend group functionality that can participate in hydrolysis andcondensation reaction with silanol groups of PMMSQ nanoparticles. Somespecific silane coupling agents of interest include aminopropyltriethoxy silane, mercaptopropyl triethoxy silane, and perfluoro alkyldimethyl chlorosilane.

The solution is vortexed to facilitate uniform reaction of the couplingagent with the dispersed nanoparticles in the solution. The couplingagent is allowed to react with nanoparticles for a period of one hourduring which the initially clear solution turns milky. TMCS basicallyreacts with the surface—OH groups present on the PMSSQ nanoparticlesmaking them further hydrophobic resulting in their eventualprecipitation from the ethanol. These nanoparticles can be recovered inthe form of a gelatanious precipitate through centrifugation anddecantation of the supernatant solution. The obtained nanoparticles arethen dried using nitrogen flow and can be easily dispersed in anynon-polar solvent like toluene, chloroform, etc. Using this approachbulk quantities of these nanoparticles can be obtained that can beeasily dissolved in various non-polar solvents at relatively highloadings (50-60%). The particle size ranges, for example, from about 2to about 5 nm, with a mean particle size of, for example, 3.5 nm.

The nanoparticles of the invention have a relatively large surface area.In general, the free-flowing nanoparticles have a surface area of atleast 500 m²/g. In one embodiment, the free-flowing nanoparticles have asurface area of at least 600 m²/g. For example, the free-flowingnanoparticles may have a surface area of at least 1,000 m²/g. In onepreferred embodiment, the free-flowing nanoparticles have a surface areaof about 500 to about 1700 m²/g.

As previously described, the nanoporous films may contain variouscomponents to tailor the film for a microelectronic, microbiologic orother application. Because the free-flowing nanoparticles are obtaineddirectly from the nanoporous, nanoparticulate film, the free-flowingnanoparticles may also contain any of the aforementioned metals,dielectrics, dyes, etc. to tailor the nanoparticles for use in amicroelectronic, microbiologic or other application.

Liquid Core Waveguides

Light waveguides are structures used to guide light from one point inspace to another with minimal losses. The most common design for thewaveguides shown schematically in FIG. 2 consists of a dielectricmaterial with high refractive index (core 20) surrounded by a materialof lower index of refraction (cladding 22). Light is guided in the core20 between the waveguide's inlet and outlet by means of total internalreflection. The refractive index contrast between the core 20 and thecladding 22 determines the acceptance angle cone 24 for the light beam.Rays that approach the waveguide with angles within the acceptance cone24 are guided through the waveguide, while those with angles greaterthan the acceptance cone 24 are reflected as shown in FIG. 2.

While most of the light waveguides feature a solid core, having anaqueous medium as the core has its added advantages. Research anddevelopment of highly target-specific sensors has attained a level ofparamount importance because of the burgeoning need for applications innational security, health care, the environment, energy, food safety,and manufacturing. Fluorescence-based sensing is among the most commonlyused transduction methods. These sensors utilize fluorescent dyemolecules as probes and most sensing applications are performed inaqueous solutions. Since the refractive index of water (1.33) is lowerthan most solid-state materials, the excitation of the dye andcollection of fluorescence are typically performed through either bulkoptics such as epifluorescence microscopes or evanescent coupling insolid waveguides. These two configurations impose a number oflimitations. For example, in evanescent coupling, efficiency ofexcitation and fluorescence collection is poor, resulting in lowsignal-to-noise ratio and sensitivity. Bulk optics adds additional costand makes it difficult to multiplex sensors on a larger scale. Inaddition to this, liquid core waveguides can also be applied for use inabsorbance spectroscopy and Raman spectroscopy. In Raman spectroscopy,confinement of light in the liquid core improves the efficiency of Ramangeneration. In addition, a combination of Surface enhanced Ramanspectroscopy (for example, by deposition of gold nanoparticles on thenanoporous film surface) with the waveguide design will result in evenhigher Raman signal sensitivities.

As the refractive index of water is 1.33 which is lower than mostreadily available materials, construction of a liquid core waveguidewith an aqueous core becomes a challenge. Teflon AF 1600 (n˜1.31) andTeflon AF 2400 (n˜1.29) have long been the only materials reported onbeing used as the cladding material for such waveguides. These materialshowever are not the ideal choice for these waveguides, especially inapplications for use as a bio or a Raman based chemical sensor. Teflonoffers little chance for chemical functionalization desired in mostbiosensing applications. The refractive index contrast between Teflonand water is at most 0.04 which translates to an acceptance cone of just18 degrees. For applications in biosensors and Raman based chemicalsensors, this poses a significant limitation. As the fluorescence isgenerated in all directions within the waveguide, it is advantageous forthe waveguide to have a large acceptance cone thus guiding most of thegenerated fluorescence through the length of the waveguide.

Air has the lowest refractive index among all materials (refractiveindex of 1.0). Incorporating air as the cladding material would yield awaveguide with an ultra high numerical aperture. However, designing anair-clad liquid core waveguide system would be a challenge. Thus for amore efficient liquid core waveguide bio/chemical sensor, new materialswith ultra low refractive indices have to be engineered. Nanoporous,nanoparticulate dielectrics such as in accordance with this inventionare therefore an ideal choice as the cladding material. With pores inthe order of 2-4 nm diameters, these materials have an extremely lowrefractive index. In one embodiment, refractive indices of 1.15 or lessare achieved which correspond to an acceptance cone of at least 42degrees. These dielectric materials have excellent adhesion to thecommon substrates and easy functionalization of these surfaces with wellestablished methods makes them all the more attractive for biosensorapplications. The large refractive index contrast between the aqueousmedium (1.33) and the nanoporous dielectric film (1.10-1.13) results ina large acceptance cone as compared to Teflon AF (1.29). Thus shorterchannels can be used in applications such as Raman based sensors andfluorescence based biosensors.

Surface modification of these films can be performed by well establishedprocesses, unlike Teflon AF based materials, which is an importantrequirement in biosensor design. A further attractive aspect of theinvention with respect to biosensors is the rapid formation of ultra-lowrefractive index, low stress, crack free and smooth films based onorganosilicate. The fabrication methodology of these nanoporousdielectric films makes them readily amenable to mass productionmethodologies. In one embodiment, the as-formed films are highlyhydrophobic thus no further treatments are necessary to avoid waterseepage into the pores and the eventual degradation of the films.

One aspect of the present invention, therefore, is a compact,microfabricated chip based liquid core waveguide (LCW) system employingnanoporous dielectric coatings as the cladding material. Conventionalmicrofabrication of liquid core waveguides involves etching channels insilicon/glass followed by coating of a low refractive index dielectricmaterial and subsequent bonding with a similarly processed glasssubstrate. Integration of these nanoengineered materials in the liquidcore waveguide design is a challenge. Unlike Teflon where thick filmscould be formed within the etched channels, forming thick nanoporousorganosilicate coatings results in a largely stressed film whicheventually cracks. To circumvent these issues, a modification has beendone in the basic design of the liquid core waveguides in which thesidewalls are eliminated. The new design of device 30 in FIGS. 3 and 4relies on interaction of water with patterned hydrophobic regions 32 andhydrophilic regions 34 on substrates 36. The patterned hyrdrophobic andhydrophilic regions are the nanoporous, nanoparticulate films of theinvention having a refractive index of, e.g., 1.10. In this design, asubstrate is patterned such that it consists of super hydrophilicchannels 44 (e.g., water contact angles of <20 degrees) separated bysuper hydrophobic regions 42 (e.g., water contact angles of >90degrees). Such a layout forces water 38 to be confined within thehydrophilic 44 regions of the substrate. Two such substrates 36 arepatterned and held on top of each other with some spacers 40 of, e.g.,teflon in between.

As shown in FIGS. 3 and 4, when water 38 is introduced at one end of thechannel by placing a drop, the hydrostatic force together with thesurface tension of the hydrophilic top and bottom surfaces suck thewater to fill the hydrophilic channels 44. The hydrophilic channel 44 inFIG. 4 separates two hydrophobic regions 42, all being between thespacers 40. The hydrophilic channel 44 contains the water with arefractive index of 1.33; the hydrophobic channels 42 contain air with arefractive index of 1.0; and the hydrophobic regions 32 and hydrophilicregions 34 on substrates, being formed from the nanoporous films of theinvention, have a refractive index of, e.g., 1.1. Water that is presentat the hydrophobic end experiences a force in the opposite direction dueto surface tension. As long as this force is larger than the hydrostaticforce that is acting to push the water in, the water will not be able toenter the hydrophobic regions. Thus, it is possible to confine the water38 only in the hydrophilic channels by this design, in effect having acolumn of water that can serve as a waveguide. FIG. 3 shows twohydrophilic channels defined by the hydrophilic regions 34; but for easeof illustration, FIG. 4 shows just one hydrophilic region 44.

Optical Fiber Waveguides

High numerical aperture (NA) optical fibers are increasingly becomingattractive for medical illumination applications as they provide forbroad irradiation patterns enabling the use of small diameter fibers forminimally invasive surgeries. Apart from minimizing the modificationsneeded to disperse output patterns, these fibers allow lower bend radiuswithout introducing significant losses due to large bends. The powerrequirements of the lamp source are also greatly reduced as the highacceptance angle associated with these fibers accepts greater percentageof light compared to a low NA optical fiber.

Conventional optical fibers, although designed to be low loss, sufferfrom having low numerical apertures. Increasing the refractive indexcontrast between the core and cladding of the optical fiber increasesits numerical aperture. This can be accomplished by choosing materialswith very low refractive indices to function as the cladding material.However, most of the readily available solid state materials haverelatively high refractive indices. Nanoporous dielectric coatings offera unique opportunity to address this issue. Refractive indices as low as1.10 (compared to 1.46 of a typical cladding material) can be obtainedby packing different volume ratios of air pockets in the matrixmaterial. However, adapting these coatings to the fiber optics ischallenging. Existing fabrication processes to obtain these coatings areusually time consuming and require tight heating/cooling cycles makingit difficult and uneconomical for practical application.

One challenge is that once the coatings have been applied on thesubstrates, in order to obtain crack-free porous films, extremely slowtemperature ramp-up/ramp-down times (of the order 1° C./min) are used.This places a serious constraint on the adaptability of these coatingsfor optical fiber manufacture especially while integrating it with theconventional optical fiber manufacturing techniques.

Another challenge associated with these coatings is stability to thermalshocks. Beyond a certain thickness (˜1 micron) the films are extremelysusceptible to cracking introduced due to thermal stresses. Opticalcoatings >1 micron thickness are usually required for waveguideapplications to confine most of the propagation modes within the fibercore.

Accordingly, nanoporous, nanoparticulate coatings of the presentinvention are ideal for this application. Apart from rapid formation ofthese films, with an annealing time typically between about 3 and about5 minutes after film deposition, these films are stable to temperatureshocks resulting from the fast heating and cooling cycles forcuring/calcinations process. The obtained coatings are hydrophobic innature and thereby resist moisture absorption and subsequent filmdegradation. Furthermore, the chemical precursors required for thepreparation of these films are inexpensive, making this an economicalsolution to produce high numerical aperture optical fibers compared toother methods. These coatings can be directly adapted with thetraditional fiber optic manufacturing techniques to yield optical fiberswith high numerical apertures.

It is therefore seen that fiber optics with silica core andorganosilicate thin film as cladding has large acceptance angle and thusthese optical fibers can be used for applications needing largenumerical apertures to collect the maximum light possible. Such opticalfibers find use in medical illumination applications. Numericalapertures as large as 0.9 can be achieved with the use of such coatingsas cladding.

High Surface Area Substrates for Chemical-Biological Assays

The high surface area associated with the nanoporous, nanoparticulatefilms of the invention can be utilized for chemical-biological assaysfor increased density of binding to enhance sensitivity. Because of thenanoparticulate nature of the film together with the presence ofnanopores, these films feature a high surface area (e.g., >500 m²/g),thus enabling for a greater density of immobilization of biologicalprobes and thereby enhancing the sensitivity. The large surface area canbe used for chemical and biological sensor platform to enhance thedetection sensitivity. Also, organosilicate particle surface can beeasily modified to provide chemically-accessible hydroxy groups (e.g.,by oxygen plasma or ozone treatment) for bonding with biologicalmolecules. Advantageously, these films are transparent over the visiblespectra and provide a greater density of immobilization, translatinginto a higher signal to noise ratio, for example, in fluorescence basedbiosensing.

Imaging

The formation mechanism of the films and nanoparticles can be controlledto incorporate fluorescent dyes, metal nanoparticles intercalated withinthe organosilicate nanoparticles, as discussed above. Fluorescentdielectric nanoparticles, for example, are biocompatible, thus enablingtheir use for in vivo imaging applications.

In this application, dye-doped nanoparticles are formed in a mixedsolution of good and bad solvent. There are two ways to extract thenanoparticles as discussed above, one of which is precipitation from thesolution, and the other of which is by making a thin film of thesolution. In the first method, nanoparticles formed in solution arecollected by centrifuge. In the second, more preferable method, there isthin film formation since it provides freedom for surface modificationby plasma treatment, which is an essential step to create carboxyl oramine groups on the surface of the nanoparticles for biologicalapplications, while dye-doped nanoparticles have methyl group onsurface. Once a thin film is obtained by, e.g., spin coating, it isannealed at high temperature depending upon the dye bond in the particleto remove free dye on the surfaces of nanoparticles and enhancecrosslinking of nanoparticles. In this annealing step, the role of theporogen (bad solvent) is crucial for preventing inter crosslinking amongnanoparticles. For rhodamine 6G doped nanoparticles, 250° C., forexample, is optimal. The annealed films are then treated with plasma torender the nanoparticle surfaces hydrophilic so as to disperse theparticles in water for biocompatibility. Oxygen plasma is used to createcarboxyl groups for the nanoaprticles. For example, ATR spectra haveshown COOH groups at 1720 cm-1 after oxygen plasma treatment. Otherplasmas such as ammonia, nitrogen and carbon dioxide plasmas are usedfor other purposes. The plasma treated films are then scraped anddispersed in water. The size of nanoparticles may vary, for example,from 3 nm to 10 nm as demonstrated by TEM imaging, depending upon —OHcontents in the PMSSQ. The dye-doped nanoparticles from this synthesisare very photostable. The reason is that the dyes trapped insideparticles (hydrophobic core) have an outside protection layer(hydrophilic shell). The hydrophobic core/hydrophilic shell structure isdue to hydrophobic nature of PMSSQ and carboxyl group on surface afteroxygen plasma. Photobleaching of R6G-doped nanoparticles and pure R6Gnanoparticles at an emission wavelength of 581 nm has shown highphotostability after 30 minutes continuous exposure to 10× lens under130 W mercury lamp.

Other Applications

Inasmuch as one aspect of the present invention is a process for therapid formation of ultra-low refractive index, low stress, crack freeand smooth films based on organosilicate, the method, films, andnanoparticles have application elsewhere where its features such as highporosity, low refractive index, and the like are applicable. Thefabrication methodology of these nanoporous dielectric films makes themreadily amenable to mass production methodologies. As noted, theas-formed films are highly hydrophobic thus no further treatments arenecessary to avoid water seepage into the pores and the eventualdegradation of the films. For example, these films can also be appliedfor use as low-k dielectrics in semiconductor industry for siliconmicrochip technology, as well as, organic thin film transistors. Theyalso have thin film laser application. In nanorod form, thenanoparticles may be used as bioscaffold material for tissue repair.

The following examples illustrate the invention.

Example 1

For the preparation of films, polymethylsilsesquioxane (PMSSQ) having amolecular weight, M_(n), of 6000-9000 (Techneglas; Perrysburg, Ohio;Gelest, Inc; Mossisville, Pa.), poly(propylene glycol) (PPG) having amolecular weight, M_(n), of 424 (Sigma-Aldrich; St. Louis, Mo.) andpropylene glycol methyl ether acetate (PGMEA) (Sigma-Aldrich; St. Louis,Mo.) were used as supplied. A 50% by weight solution of PMSSQ wasprepared by dissolving 5 g of PMSSQ in 5 g of PGMEA and designated assolution A. This solution was then filtered using a 0.25 micron filter.A 50% by weight solution of PPG was prepared in PGMEA by dissolving 5 gof PPG in 5 g of PGMEA and designated as solution B. Solutions A and Bwere then sonicated separately for at least 10-15 minutes to ensurecomplete dissolution of the respective solutes. After obtaining clearsolutions, Solution A was mixed with solution B and sonicated for anadditional 5 minutes to obtain a homogenous solution. This solution wasthen taken in an open beaker and placed on a hot plate at 70° C. underconstant stirring (600 rpm). The weight of the solution was continuouslymonitored and the solution was removed from the hot plate after apredetermined amount (0.5 g, 1 g, 2 g and 6 g) of the PGMEA wasevaporated. The resulting clear, viscous solution was then transferredinto a glass bottle and sealed for further use.

This dispersion was then spin cast onto silicon substrates to form thinfilms (2 micron thickness). Immediately after the spin coating, thefilms were calcinated on a hot plate at 470° C. for 5 minutes for PPGburn out resulting in the nanoporous film. In addition to serving as apoor solvent, the PPG molecules act as a plasticizer during the finalfilm formation resulting in a low stress, crack free film. The obtainedfilms could withstand the large thermal stresses resulting frominstantly stepping down to room temperature from 470° C. FIGS. 5A and 5Bshow the cross-sectional SEM of the film along with the magnified view.From the figure it can be seen that the film is smooth and is comprisedof nanoparticles with a narrow size distribution in the range 2-3 nm. Itcan also be seen that it is possible to control the size of thenanoparticles by using different Si—OH content PMSSQ varying the initialcompositions of the solution, amount of the solvent evaporated, and thetemperature at which the evaporation is carried out.

Electrical characterization of these films has been performed in a probestation on the metal/insulator/metal (MIM) structures at roomtemperature. Capacitance-voltage (C-V) measurements were carried outusing an HP 4284A LCR meter at frequencies 100 kHz and 1 MHz. Nanoporousdielectric films were deposited on heavily doped, electricallyconductive silicon substrates from one day aged solution. Aluminum dotswere then sputter coated on these films through a shadow mask.Dielectric constant measurements performed in this manner gave a valueof 1.4 at 100 KHz and 1.42 at 1 MHz. Optical characterization of thesefilms was carried out by variable angle spectroscopic ellipsometry(VASE™, J. A Wollam, Inc.). Ellipsometric measurements were taken on theporous films at 65° and 75° incident angles with wavelength scansperformed from 300 nm to 1700 nm. For the data modeling, Cauchy modelwith non-idealities was used to fit the data. The details of themodeling of nanoporous organosilicate films are described in M. T.Othman, J. A. Lubguban, A. A. Lubguban, S. Gangopadhyay, R. D. Miller,W. Volksen, H.-C. Kim, J. Appl. Phys. 99, 083503 (2006). The porosity ofthe films has been modeled using the Maxwell Garnet Effective mediumapproximation model which gave a porosity of about 70% for these films.Refractive index measurements of the films gave a value of 1.10 with athickness of 884 nm. FIGS. 6A and 6B show the fitting curve as well asthe depth profile of the film from the graded Cauchy and non ideal modelfit.

Nanoindentation technique (Tribolndenter, Hysitron Inc.,) was used tostudy the mechanical properties of the film. From the nanoindentationmeasurements, the modulus of elasticity of the film has been calculatedto be 0.56 GPa. It is well documented that the modulus of the nanoporousfilms drop rapidly with increasing porosity. Thus in comparison to thenanoporous dielectric films prepared by the porogen approach of the sameporosity (70%) these films are higher in modulus and expected to be morerobust. Apart from the good thermal stability (up to 500° C.) thesefilms have shown to have good adhesion to common substrates (Silicon andPyrex glass). Thus, these films can be used as low-k material in Siliconback-end process as well as a gate dielectric for thin film transistors.Such low-k materials are increasingly becoming attractive for use asdielectrics in organic field effect transistors.

Example 2 Physical Characteristics

Nitrogen adsorption-desorption isotherms for samples prepared asdescribed in Example 1 were analyzed using a Quantachrome Autosorb-1automated gas sorption system and the surface areas of the samples werecomputed using BET method. For the analysis, films were prepared onsilicon substrates from one day aged solutions. The nanoparticulatepowder was obtained by carefully scraping the film from the substrate.Since the samples are hydrophobic, these were degassed at roomtemperature for twelve hours. The isotherms obtained for these filmsshown in FIG. 7A are classified as Type IV, as normally observed intypical mesoporous samples (pore size of 2-50 nm as defined by IUPAC).However, it is seen that that there is a sharp increase of the volume ofnitrogen adsorbed at relative pressures (P/P_(o)) in the range of10⁻⁷-10⁻⁴. Therefore, it is expected that these samples are likely toexhibit both microporosity and mesoporosity.

The BET plots shown in FIG. 7B reveal that the surface area of thesenanoparticulate porous films prepared using PMSSQ precursor with 2% and14% OH content are 657 m²/g and 1325 m²/g respectively. The high surfacearea of these samples is attributed to the large amount of pores createdby the removal of PPG, voids between the nanoparticles and extremelysmall size of these nanoparticles with a narrow size distribution.Smaller nanoparticles with the size range of 10-14 nm were observed infilms prepared using PMSSQ precursor with 14% OH content in comparisonwith that of 20-40 nm sized particles observed in films prepared with 2%OH content.

High surface area porous silica materials reported in the literature areconventionally hydrophilic and therefore those samples requirepost-treatments with silylating agents like TMCS, HMDS etc. In contrast,the process of the present invention yields high surface area,hydrophobic porous silica nanoparticles in a single step synthesisprocedure.

T-plot analysis of the isotherms was performed to determine the amountof microporosity in the samples. T-plots shown in FIG. 8A revealpositive Y-axis intercept for both these samples. The de BoerStatistical Thickness on the x-axis is in angstroms. The obtainedmicropore volumes for films prepared using precursors with 2% and 14% OHcontent are 0.03 cc/g and 0.006 cc/g respectively. The microporosity inthese samples constitutes 2.3% and 0.4% of the total pore volumeobserved. For the sample prepared with 2% OH content in MSSQ precursor,the micropore surface area of 80 m²/g and the external surface area of577 m²/g add up to 657 m²/g which equals the BET surface area.Similarly, for the sample prepared with 14% OH content in MSSQprecursor, the micropore surface area of 42 m²/g and the externalsurface area of 1273 m²/g add up to 1315 m²/g, which is very close tothe total surface area of 1325 m²/g obtained from BET analysis.

Pore size distribution was determined applying the density functionaltheory and Monte Carlo simulation methods using the AS1 WIN softwarepackage. The pore size distributions (FIG. 8B) reveal that the microporemode is about 1.5 nm for both the samples. The size distribution ofmesopores lies in the range of 3-9 nm in case of smaller nanoparticles(10-14 nm) prepared with 14% OH content in PMSSQ precursor and it liesin the range of 3-16 nm in case of larger nanoparticles (20-40 nm). Thetotal pore volume obtained for samples prepared with 2% and 14% OHcontent in MSSQ precursor are 1.32 cc/g and 1.5 cc/g respectively. Thelarge amount of porosity exhibited these organosilicate hydrophobicfilms is attributed to the removal of PPG and the voids formationarising from the assembling of the nanoparticles on the substrate at thetime of film deposition.

Example 3 Nanoparticulate Films

Nanoparticulate films were prepared by spin deposition onto freshly 1:10HF:DI dipped silicon substrates followed by a heat treatment step of 400C for 5 minutes, using the procedures described in Example 1 except asotherwise noted. These films were prepared with 14% OH content PMSSQfrom Techneglas Inc, (GR650F). The films were prepared with one day agedsolution. FIGS. 9A and 9B depict the SEM of the film's cross section.The films prepared from 2% OH content PMSSQ (Gelest, SST-3M02), on theother hand, gave nanoparticulate films with particle sizes ˜40 nm (seeFIG. 7). The difference in particle size between the 14% (Mw 5000) andthe 2% PMSSQ (7000-8000) may be due to the differences in molecularweight between the two different PMSSQ. 2% OH content solutions tend totake longer time to gel because of the presence of less number ofreactive sites.

Example 4 Nanoparticulate Dispersions

A dispersion of organosilicate nanoparticles was prepared by scraping afilm prepared as described in Example 1 with a flat razor blade,collecting the resulting fine powder and dispersing it in a surfactantsolution via sonication. The resulting solution was then filtered with a0.2 micron filter to obtain a clear nanoparticle dispersion. FIGS. 10A,10B, and 10C are TEM images of the resulting organosilicate nanoparticledispersions. The scale bars are 1 micron, 200 nm, and 500 nm,respectively in A, B, and C.

Example 5

Nanoparticles were obtained directly from a gel prepared as set forth inExample 1 except that the gel was treated with n-hexane. n-Hexanetreatment of the gel results in an effective dehydration of the gelthereby freezing the crosslinking reactions occurring within the gel.Solutions were poured into glass Petri dishes and allowed to gel. Thegels were later soaked in hexane for a 12 hour period following whichexcess Hexane was decanted. FIG. 12 shows the ATR-FTIR spectra of thehexane-treated and not treated-gels aged the same time.

Although the gels were aged the same time, in the case of the hexanetreated gel, the extent of cross linking (evident from the twin peaks inthe region 1100-1000/cm) is considerably reduced. Also, regular gelscrack over time as the gel shrinks, oozing out the solvent and PPG inthe process and gets densified. This was not observed in the case of thehexane treated gel.

In order to crosslink the particles fully before extracting them fromthe gel, the gel was placed in a conventional microwave oven andmicrowaved for 5 minutes. Microwaving regular gels under similarconditions results in a phase separation between the liquid and thesolid parts; this appears to be due to the accelerated interparticlecrosslinking within the gel. However, this behavior was not observed forthe hexane treated gels suggesting that the microwave treatment resultedin the intra particle crosslinking while the particles remainedseparated from each other. No cracking of the gel was observed evenafter the microwave treatment. FIG. 13 shows the ATR-FTIR spectra of themicrowave-treated gel.

Extraction of the particles from the gel was accomplished by crushingand grinding the microwave treated gel and dissolving the resultantwhite powder in surfactant solution. The solution was filtered with a0.2 micron filter to obtain a clear dispersion. FIG. 14 gives the TEM ofthe obtained particles, with the scale bar being 100 nm. As can be seenfrom the TEM, there are bigger particles possibly due to agglomerationas well as smaller particles 10 nm (same size as obtained from films).

Example 6 Organosilicate Nanorod Networks Nanoporous OrganosilicateNanorods

It has been observed that aging of the nanoporous organosilicateprecursor solutions at ambient conditions results in the formation ofgel with time. The gelation occurs within 7 days time and is stronglydependant on the amount of the evaporated solvent as well as the amountof —OH content in the PMSSQ starting material. Greater the amountevaporated, quicker the solution gels. Increased —OH content in thePMSSQ starting material results in a quicker gelling precursor solution.The gels have been dried to remove all the solvents and washed andfiltered with ethanol to remove most of the PPG. These gels are latersubjected to calcinations to result in a fine white powdery substance.When examined under a TEM, it has been observed that the white substanceconsists of a network of nanorods which can be separated if sonicated ina suspension.

Nanorods and nanorod networks can be obtained from the gels by aging thegels sufficiently to let the nanoparticles come together and formnetworks. The gels are crushed and washed repeatedly with ethanol toremove excess PPG and calcined to remove the PPG and fully crosslink thenetwork. The obtained powders are later sent for microtoming to beobserved in TEM. FIG. 15 gives the TEM of the microtomed samples. FIG.15A (scale bar=500 nm) is from a dense gel aged for a long time while15B (scale bar=200 nm) is from a fresh gel.

Example 7 Substrate Surface Dependant Properties of the Films PlasmaTreatment of Nanoporous Silicate Films

Low power oxygen plasma treatment of a primary nanoporous organosilicatefilm followed by deposition of a secondary organosilicate film has beenfound to collapse the pores of the secondary coating. In a typicalprocess, a thinner film of the primary coating is applied first and heattrated to 470° C. for 2 minutes. This film is later treated to a lowpower oxygen plasma treatment and immediately a secondary nanoporousorganosilicate film (thicker film, no dilution) is spin coated over theprimary film and processed at 470° C. for 5 minutes. It has been notedthat the dielectric properties of the nanoporous silicate films for thefilms prepared on plasma treated nanoporous silicate surfaces isaltered. The refractive index of the films has been found to increase tothe inherent refractive index of the organosilicate films suggestive ofthe collapse of the pores.

Table gives the refractive index and thickness values of films preparedby normal deposition process and on plasma treated nanoporous silicatesurface. The hydroxy groups on the substrate surface have been shown tohave an effect on the dielectric as well as the optical properties ofthe final film.

TABLE 1 Refractive index and thickness of films with and withoutadhesion layer Adhesion Annealing Refractive Sample layer conditionsThickness index 1 No Hot plate 760 nm 1.149 470 C. 5 mins 2 Yes Hotplate1150 nm  1.37 470 C. 5 mins Adhesion Hot plate 201 nm 1.38 layer 470 C.5 mins

Similarly, the coatings on glass substrates have been shown to yieldfilms with properties different from those deposited on siliconsubstrates. Films deposited on piranha treated glass substrates havebeen shown to exhibit higher refractive indices than films deposited onglass substrates cleaned with organic wash.

Example 8 Dye Incorporated Organosilicate Nanoparticles

Two solutions (solution of 50% by wt PMSSQ in ethanol and 50% by wt PPG424 in ethanol) were prepared first as described in Example 1. Rhodamine590 (0.024 g), a dye, was introduced into solution containing PMSSQ andsonicated to ensure complete dissolution. The solutions were mixedtogether and subjected to an evaporation step by heating it in an openbeaker under stirring at 70° C. Approximately 10% of the solvent wasevaporated, and the combined solution was transferred to a bottle,sealed and allowed to cool to room temperature. To obtain thenanoparticles, the combined solution was spin coated onto silicon/glasssubstrates and heated at 250° C. for 30 seconds to further crosslink thePMSSQ nanoparticles and partially burn-out the PPG.

If desired, the surface functional groups which are predominantly Si—CH₃can be readily modified to Si—OH or Si-carboxy groups by subjecting thefilms to a brief low power oxygen plasma treatment step (for example, 2minutes of exposure to a 6 W oxygen plasma). Other plasmas like ammoniaplasma creates Si-amine groups. The hydroxy, carboxyl, or amine groupsmay then be used for immobilization of bioprobes or other functionalmoieties. The films may then be scraped off and redispersed in DI waterfor further use.

The choice of dyes depends on the charge on the dyes. For example,rhodamine 6G has a positive charge in solution. Most of rhodamineprospects and derivatives such as rhodamine 560, 575, 590, 610 and 640and 6-Carboxyl-X-Rhodamine (ROX), Tetramethyl-6-Carboxyrhodamine (TAMRA)and Tetramethylrhodamine-5-(and-6)-isothicyanate (TRITC) are suitablefor this requirement. Other dyes include, for example, cyanine (cy 3, cy5 and cy 7), HIDC, LDS 698, oxazines (oxazin 720, 725, and 750), TexasRed, DvLight Fluors, HvLight Fluors, Alex Fluors, etc. Moreover, a dyewithout any charge could further be modified to have a positive chargeby doping it into the nanoparticles. Dyes that may be treated in such amanner include, for example, Coumarins (Coumarin 440, 445, 460, 480 and481) and their derivatives (7-Hydroxycoumarin-3-carboxylic acid,7-Hydroxycoumarin-3-carboxylic acid, etc.), fluorescein isothiocyanate(FITC), etc. The dye itself is not particularly critical to theinvention, and such dyes are well understood in the art, such as fromU.S. Pat. No. 7,169,584 (Tables 1 and 2).

Example 9 Conjugation of Nanoparticles with Antibodies

Nanoparticles containing rhodamine 590 or other dye and derivatized tocontain carboxy or hydroxy groups as described in Example 8 may belinked to antibodies (polyclonal, monoclonal, or functional fragmentsthereof) or other biological molecules. Antibodies may be linked to theparticles, for example, by reaction of the carboxyl groups present onthe nanoparticle with amino groups of the antibodies, for example, by astandard method employing EDC and Sulfo-link (from Pierce Biotechnology)to conjugate the nanoparticles to specific antibodies. The resultingbond is a relatively strong and stable bond with minimal distancebetween the antibody and the fluorescent particle rendering the particlesuitable for cell internalization. FIG. 13 depicts a reaction scheme forproducing the conjugates.

Preliminary studies using an antibody against the laminin-1 in chickhearts showed an unexpected increase in fluorescence efficiency. Thisantibody is normally used in a standard two-step procedure where optimalconditions have been reported a 1:250 dilution of the primary antibodyin an overnight incubation protocol, followed by the uses as a secondaryantibody. With conjugation of the primary antibody to a particle filledwith Rhodamine 590, at least 1000-fold increase in fluorescence wasobserved. Pairs of tissues at room temperature were able to be stainedfor 30 minutes with 1:250,000 dilution, without loss of resolution (seeFIG. 17). A graph depicting the time dependant decay in fluorescence ofa tissue stained with the antibody conjugate appears in FIG. 18.

To further evaluate the stability of the fluorescence particles overlong periods of time, a single slide was exposed under a 150 W Hg lampfor 6 continuous hrs. Three pictures were taken every hour, and the meanpixel intensity for each picture was evaluated and averaged. This isshown in FIG. 19. Rhodamine typically exhibits a marked rapid bleaching(reduction of fluorescence intensity which depends upon the intensity ofthe light source and the exposure time); in this study, however, thetissue immune-staining with the antibody, conjugate with ournanoparticles, exhibited an extremely low degree of bleaching.

Example 10 Conjugation of Nanoparticles with Biologics

To better understand the effects of clustering or binding materialsinside or in the surface of our nanoparticles/rods, several differentcrosslinkers were tested. Preliminary data show an effectivecrosslinking of nanoparticles with antibodies using a two stepEDC-sulphoNHS system. The resulting complex results in the formation ofa stable and strong linker between the nanoparticles and the antibodywith an amine group. However, in different conditions, other types ofcrosslinkers could be necessary to combine different pharmaco-compoundswith our particles. These crosslinkers should be able to react with alarge arrangement of reactive groups and with different lengths/sizes.

For example, dye-doped nanoparticles could be linked to compounds on thesurface of the particle/rod and antibodies simultaneously. Theapplication of this complex into a system will allow the binding of theantibody with a specific cell/tissue type, the dye inside of theparticle will be useful to visualize the target and the compoundattached to the rest of the particle could be used to treat or modifythe cell. This complex series of interactions could be useful in thetreatment of diseases, such as, for example, cancer, where a particlecould be crosslinked to a specific antibody or peptide that recognizesprimarily the material specifically expressed on the surface of thecancer cells. Once the particle is localized on the surface of thecell/tissue, a shock wave generator can be employed to propel thenanomaterials inside the cells where their cargo, inside or on thesurface of the nanomaterial, could be delivered to the cell/tissue.Another possible alternative is to dope the nanoparticles withbiological crosslinkers. These sequences of amino-acids (crosslinkers)could be degraded by enzymes that are inside the cells, allowing therelease of their cargo. A similar system has been used to efficientlytransfer and deliver fluorescent dyes, such as Fura 2-AM, BCECF AM, etc.These materials carry acetoxymethyl (AM) and acetate esters. Themodification of the carboxylic acids with AM ester groups results in anuncharged molecule that can permeate cell membranes. Once inside thecells, the lipophilic blocking groups are cleaved by nonspecificesterases that leak out of cells more slowly than their parent compound.Frequently, hydrolysis of the esterified groups is essential for bindingof the target ion. In some cases, the AM ester is colorless andnonfluorescent until hydrolyzed (e.g., calcein AM). This property isuseful in diagnosing spontaneous hydrolysis during storage.

Example 11 Fabrication of the Liquid Core Waveguide

Teflon was used as the hydrophobic coating. Patterning of Teflon wasaccomplished through an aluminum liftoff process described in detailbelow. Nanoporous organosilicate films were first deposited on siliconand amorphous silicon (<5 nm) coated borosilicate glass substrates. A10s HF (10 DI: 1 HF) dip was performed immediately prior to thenanoporous organosilicate coatings on silicon to remove the nativeoxide. A 300 nm thick aluminum film was later sputter coated on thenanoporous organosilicate coated substrates. The patterning of thechannels was performed on the aluminum layer so that the underlyingnanoporous organosilicate film was not exposed to photoresist at anyinstant of time during the whole process. Channel patterns werefabricated on top of the aluminum coated substrates using a positivephotoresist (S1813). The masks for the fabrication of the channels isshown schematically in FIG. 20. The channels fabricated were 500 micronin width. The thick bars on either end (1 mm wide) were used foralignment of the bottom (silicon) to top (glass) substrates for thefinal device.

The fabrication flow chart for the process is given in FIG. 21, with thesilicon substrate at 210 and the glass substrate at 212. After thepatterning of photoresist with the above masks, the substrates weredipped in an aluminum etchant solution (85% Phosporic acid, 5% Nitricacid, 5% acetic acid, 5% DI water at 70 C) to pattern the aluminum. Atthis point, the channels to be used for the liquid core waveguide arethe regions containing aluminum channels. Photoresist was then washedoff with acetone following the aluminum etch.

Teflon Film Deposition

Patterning Teflon can be challenging as the surface of Teflon has suchlow surface energy that no material readily sticks to it, includingphotoresist. Thus, the lift-off process for Teflon patterning wasemployed. Since aluminum was used instead of photoresist for the liftoff process and as it is uneconomical to have very thick films ofaluminum (>1 micron) to achieve lift off, an ultra thin coating ofTeflon (<10 nm) was used so that the lift-off process could be performedwith a 300 nm thick aluminum patterns. The aluminum patterned substratesfrom the previous step were first coated with a thin (monolayer) of FSM(fluoro silane coating, FSM 660, 3M Corp.) and baked at 95 C for 10 minsas prescribed by the manufacturer. A 0.05% Teflon solution (Teflon AF1600) was prepared in FC 75 solvent (3M Corp.) and films were spincoated at 3000 rpm for 30s to obtain ultra thin coatings of Teflon (<10nm thick). A 0.5% Teflon coating prepared in similar way gave athickness of 40 nm. The surface properties are characteristic of Teflonsurfaces, having contact angles with water ˜120 degrees. The substrateswere then heated at 135° C. for 5 minutes, 225° C. for 5 minutes and300° C. for 10 minutes to cure Teflon and improve its adhesionproperties with the substrates. After the heat treatment step, thesubstrates were allowed to cool down before being taken off from the hotplate for further processing.

The Teflon coated substrates were later dipped in the aluminum etchantsolution to lift off aluminum thereby pattering Teflon. Thus, in effect,the substrate has been patterned with hydrophobic—hydrophilic regionswhere the hydrophilic regions (channels) will be utilized for the liquidcore waveguide.

Spacer Fabrication

For the initial prototype design, PDMS spacers were fabricated and used.For the future devices, SU 8 spacers will be utilized such that the SU 8waveguides coupling the liquid core waveguide as well as the spacerswill be defined in a single lithography step. For the fabrication of thePDMS spacers, an adhesive tape of known thickness was used and stuckaround the perimeter of a glass substrate. 1:10 PDMS mix was then pouredinto the well. Excess PDMS was carefully removed by traversing a flatblade across the surface of the glass substrate such that the level ofPDMS in the well was flush with the top of the adhesive tape. Thus, thethickness of the spacer is defined by the thickness of the adhesivetape. PDMS was chosen in this case as the surface of PDMS is tacky whichwould prevent substrates from moving once they were aligned.

Characterization of the Liquid Core Waveguide.

Loss characterization of the waveguides was performed by filling thechannels with a 0.05 mM concentration flourescien dye. Approximately 10microliters of the dye was taken introduced into the hydrophilicchannels of the waveguide. Capillary action from the hydrophilicchannels together with the hydrostatic force pushes the solution tocompletely fill the channels. The channels were transversly illuminatedwith a Blue LED light (470 nm wavelengthh). A microscopic objective(20×) was used to focus the light onto the channels. The excitationsource was moved through the length of the waveguide and thefluorescence counts were recorded using a spectrometer (Ocean Optics,USB 4000). A 600 micron core fiber optical cable coupled to one end ofthe channels was used to collect the fluorescence signal from thewaveguide into the spectrometer. For these experiments, a PDMS spacerhaving a thickness of 150 microns (as defined by the adhesive tape) wasused.

FIG. 22 illustrates the experimental set-up for loss characterizationand waveguide effect is illustrated in FIG. 23. The waveguide wasilluminated transversally and the illumination source was moved acrossthe width of the device traversing three liquid channels in the process.The plot of the loss characteristics of the waveguide is shown in FIG.24. From the plots, the waveguide loss has been calculated to be about0.5 dB/cm. Further reduction in the loss can be accomplished by the useof a high quality hard mask for patterning purposes.

Example 12

Dielectric constant and refractive index measurements were performed onthese films at different processing (calcination) temperatures. It wasobserved that the temperature of calcinations played an important rolein determining the dielectric constant (and refractive index) of thefinal films. Two types of PMSSQ precursors were used (2% OH contentPMSSQ from Gelest, Inc, and 14% OH content PMSSQ from Techneglas).Solutions of PMSSQ and PPG in PGMEA were prepared in different ratios:PPG: PGMEA ratios of 3:7 and 5:5 were used, PMSSQ:PGMEA ratios of 3:7and 5:5 were used. Solutions designated 7:3 are the ones obtained bymixing 3:7 PPG:PGMEA solution with 3:7 PMSSQ:PGMEA solution in 1:1ratio. Similarly the solutions designated 5:5 are the ones obtained bymixing 5:5 PPG:PGMEA with 5:5 PMSSQ:PGMEA solutions. Furthermore, thesesolutions were either subjected to an evaporation step (films producedthereof designated as w/evaporation, see details of the NPO precursorsolution preparation in previous sections) or no evaporation prior tofilm deposition. It was observed that regardless of evaporation ordilutions, nanoparticle formation was evident in all the cases. FIGS. 25and 26 are SEM micrographs of the resulting nanoparticulate (NPO) filmsfrom the 14% OH precursor. FIGS. 25 A, C, and E were obtained from the5:5 solutions with evaporation; Figures B, D, and F without evaporation.FIG. 26A was obtained from the 7:3 solution with evaporation; FIG. 26Bwithout evaporation.

FIGS. 27 and 28 give the thickness, refractive index and dielectricconstant of the obtained films from the 2% OH precursor (FIG. 27) andthe 14% OH precursor (FIG. 28) processed in different ways as a functionof annealing temperature. FIG. 27A is the thickness of the 7:3 films (2%OH). FIG. 27B is the refractive index of the 7:3 films (2% OH). FIG. 27Cis the thickness of the 5:5 films (2% OH). FIG. 27D is the refractiveindex of the 5:5 films (2% OH). FIG. 27E is the dielectric constant ofthe films (2% OH) as a function of processing temperature. FIG. 28A isthe thickness of the 7:3 films (14% OH). FIG. 28B is the refractiveindex of the 7:3 films (14% OH). FIG. 28C is the thickness of the 5:5films (14% OH). FIG. 28D is the refractive index of the 5:5 films (14%OH). FIG. 28E is the dielectric constant of the films (14% OH) as afunction of processing temperature.

Example 13

A thin film laser without using an external cavity or constructing aperiodic spatial structure is of great interest for its potentialapplication to integrated photonic devices. Dye-incorporated porous thinfilms as prepared in accordance with Example 8 were prepared to containrhodamine 6G incorporated into organosilicate nanoparticles. Althoughthe film is porous, the refractive index (RI) of the film (RI=1.3) isstill higher than air acting as a wave guide. The film is then excitedwith a laser, and each of the dye-incorporated particles in the filmemits photons which are guided by interconnected particles. While thephotons are guided by the film, more photons are generated due tocontinuous excitation resulting in lasing effect. The circularlypatterned film is excited at different wavelengths and emits photons atthe edge as shown in FIGS. 29A and 29B. Due to waveguiding effect, nophoton is observed at the center region of the circles.

Example 14

The formation of nanorods is described and demonstrated above. A PMSSQsolution with five-day old dye incorporated therein was spin coated andannealed at 240° C. for 30 seconds. The solution was prepared asexplained in Example 8 with PMSSQ containing 2% OH. Other proceduressuch as scraping were also performed as in Example 8. The rods arelonger than 2 microns with diameters of about 50 nm as shown in FIG. 30(scale bar=0.2 micron).

Example 15 NPO Films as High Surface Area Substrates forChemical-Biological Assays

As described above, the high surface area associated with the nanoporousfilms of the invention can be utilized for chemical-biological assaysfor increased density of binding to enhance sensitivity. By thisexample, nanoporous films were prepared with 50% PPG loading, calcinatedat 550° C. to give films with refractive indices 1.13-1.15 and about 220nm thickness. The films were exposed to a low power CO₂ plasma (4 W, 1min) to obtain —COOH functionality on the particle surfaces. As acontrol, flat (non-porous) PMMSQ films were prepared by spin coatingPMSSQ solution dispersed in PMA solvent followed by heat treatment at550° C. for 5 minutes. CO₂ plasma treatment was performed on these filmssimilar to NPO films and Protein A-FITC conjugate was immobilized,following published protocol, on these substrates.

Protein A-FITC binding on the NPO surfaces and controls was evaluated atdifferent concentrations of Protein A (from 0.1 mg/ml to 1 mg/ml). FIGS.31 and 32 show the plot of the fluorescence intensity from the proteinA-FITC immobilized NPO and control substrates with 1 minute CO₂ plasmaexposure time. It can be concluded that the optimum concentration ofProtein A to yield the highest fluorescence intensity is about 0.3mg/ml. Also, compared to the control samples, a roughly two orders ofmagnitude increase in the fluorescence signal was achieved due to thehigh surface area of the nanoporous films of the invention.

For the foregoing studies, low CO₂ plasma was used to modify the NPOsurfaces to obtain —COOH groups. For initial tests, fluorescently taggedProtein A—FITC (Fluorescein Isothiocynate) conjugate was used forimmobilization in these studies. Protein A is a 40-60 kD surface proteinoriginally found in the cell wall of the bacteria Staphylococcus aureus.It has been extensively used in biochemical research because of itsability to bind immunoglobulins (i.e., antibodies). NPO films preparedwith 50% PPG loading were used for all the tests. Non porous PMSSQfilms, prepared by dissolving PMSSQ in PMA followed by spin coating andhigh temperature curing (500 C), were used as controls for the tests.Protein A-FITC immobilization was performed following published protocolfrom Pierce Biotechnology.

A two-step coupling protocol using 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDS) and Sulfo-NHS protocol was employed.EDC (2 mM) and 1.1 mg of sulfo-NHS were mixed in 1 ml activation buffer(0.1 M Mes, 0.5 M NaCL, pH 6.0). The samples were covered with thissolution and allowed to react for 15 minutes at room temperature. ThenEDS was quenched by adding 1.4 microL of 2-mercaptoethanol (Sigma,Aldrich) for 5 minutes at room temperature. Then the substrates werewashed 3 times with PBS followed by a wash with the activation buffer.Protein A-FITC (Sigma Aldrich) was diluted to different concentrationsin PBS (pH 8.5), and the substrates were immersed in this solution forat least 2 hours at room temperature or overnight at 4° C. Finally thereaction was quenched by adding hydroxylamine HCl (Pierce Biotechnology)to a final concentration of 10 nM for 5 minutes at room temperature. Theexcess quenching reagent was removed and the samples were washed 3 timeswith PBS. Measurements and storage were made in PBS+4% BSA (SigmaAldrich) to remove any unbound protein A.

The intensity of fluorescence from the Protein A-FITC immobilizedsurfaces was evaluated by using an Olympus BX51WI microscope with a 150Hg lamp and a FITC-3540B filter set “zero pixel shift” (Exciter 482+/−17nm, Emitter 536+/−20 nm Dichroic 446-500 center wavelength with abandwith of 513-725 nm—Semrock, Rochester, N.Y.). The samples wereobserved and focused using a water immersion lens LumPlanFI/IR 40×/0.80wOlympus America, Melville, N.Y.), which produces a 0.026 W/cm2 lightintensity on the surface of the sample.

The fluorescence produced by the dye in the antibodies was routed to afiber optic fiber (50 micron) coupled to a spectrometer USB-4000, underthe control of the Spectra Suite software (Ocean Optics, Dunedin, Fla.)running in a homemade PC computer. Spectra were taken from 8-10different regions of each sample and stored in the computer for furtheranalysis using Origin 8.0 (Origin, Northampton, Mass.).

Example 16 NPO—Au Nanoparticulate Films as Surface Enhanced Raman (SERS)Active Substrates for Detection of Explosives

NPO films were deposited on silicon substrates following the processdescribed above. These substrates were loaded into a sputter chamber forgold nanoparticle deposition. The percentage PPG content in theprecursor solution determines the final porosity (and the refractiveindex) of the NPO films, while the Au sputter deposition time determinesthe density of gold nanoparticles on the substrates. Raman scatteringstudies of Rhodamine 590 fluorescent dye was performed on thesesubstrates. Rhodamine dye solutions with different concentrations wereprepared and deposited on these substrates followed by solventevaporation. NPO films with 70% PPG loadings with gold nanoparticledeposition times of 2 minutes gave the best signal enhancement. Inaddition to this, it was observed that heating the NPO substratesfollowing gold nanoparticle deposition rearranges the distribution ofthe gold nanoparticles on the substrates. This was evident from theUV-Vis spectra obtained for the NPO—Au film before and after heattreatment (450 C for 60 seconds) in the reflectance mode. That is,slight peak shift along with peak narrowing could be observed for theafter heat-treated sample. An obvious color change in the substratescould be observed following the heat treatment step. Table 2 summarizesthe peak signal intensity values obtained for the Rhodamine 6Gconcentration of 10⁻⁶ M concentration on different substrates.Discernable peaks were observed for Rhodamine concentration as low as10⁻⁹ M concentration.

TABLE 2 The peak comparison table for different depositing time of Auand different condition of samples With CO2 Without CO2 treatmenttreatment NPO-w/o NPO-w NPO-w/o NPO-w Si-w/o Si-w heat heat heat heatheat heat treatment treatment treatment treatment treatment treatment Au(45 sec) 26146 4836 14279 5882 1471 601 Au (2 min) 23140 2694 3614629226 2665 12659 Au (7.5 min) 17950 36175 11393 28481 2258 0 Flat Au10059 / 4051 / 2147 /

A Raman scattering plot was generated for a) rhodamine deposited on aflat gold film on silicon, b) gold nanoparticles deposited on silicon,and c) gold nanoparticles deposited on NPO films under similarconditions. A three-fold enhancement could be observed in the case ofRhodamine deposited on NPO—Au nanoparticle substrate compared that of Aunanoparticles on flat silicon. It appears that having a stack ofmultiple layers of NPO—Au films on the substrate would greatly improvethe signal sensitivity. Accordingly, novel SERS substrates were beenfabricated combining the top-down technology (sputtered Au nanoparticlefilms) and bottom-up technology (NPO films) of the invention. Athree-fold enhancement in the SERS signal was observed in the case ofrhodamine dye deposited on NPO—Au nanoparticle substrates compared toAu-nanoparticles on flat silicon substrates.

In view of the above, it will be seen that the several objects of theinvention are achieved and other advantageous results attained.

When introducing elements of the present invention or the preferredembodiments(s) thereof, the articles “a”, “an”, “the” and “said” areintended to mean that there are one or more of the elements. The terms“comprising”, “including” and “having” are intended to be inclusive andmean that there may be additional elements other than the listedelements.

As various changes could be made in the above compositions and methodswithout departing from the scope of the invention, it is intended thatall matter contained in the above description and shown in theaccompanying drawings shall be interpreted as illustrative and not in alimiting sense.

What is claimed is:
 1. A process for the preparation of free-flowingorganosilica nanoparticles, the process comprising: forming a solutionof an organosilica nanoparticle precursor in a mixed solvent systemcomprising a first solvent and a second solvent, wherein the firstsolvent is different from the second solvent, wherein the second solventhas a boiling point which is greater than a boiling point of the firstsolvent, and wherein the nanoparticle precursor has a greater solubilityin the first solvent than in the second solvent; removing at least 50%of the first solvent to form nanoparticles having a mean particle sizeless than about 25 nanometers dispersed in the solution; adding acoupling agent to the solution to facilitate reacting of the couplingagent with the nanoparticles; and recovering the nanoparticles from thesolution, wherein the recovered nanoparticles have the mean particlesize of less than about 25 nanometers.
 2. The process of claim 1 furthercomprising, after said removing at least 50% of the first solvent,adding a coupling agent to the solution to facilitate reacting of thecoupling agent with the nanoparticles.
 3. The process of claim 1 whereinsaid removing comprises evaporation by heating.
 4. The process of claim2 comprising diluting the solution after said removing of the firstsolvent and before said adding the coupling agent.
 5. The process ofclaim 1 wherein the nanoparticle precursor comprisespolymethylsilsesquioxane.
 6. The process of claim 1 wherein thenanoparticles comprise polymethylsilsesquioxane nanoparticles.
 7. Theprocess of claim 1 comprising: forming the solution of the organosilicananoparticle precursor in the mixed solvent system comprising propyleneglycol methyl ether acetate (PGMEA) as the first solvent andpoly(propylene glycol) (PPG) as the second solvent, wherein thenanoparticle precursor has a greater solubility in the PGMEA than in thePPG; removing at least 50% of the first solvent to form thenanoparticles having the mean particle size less than about 25nanometers dispersed in the solution; and recovering the nanoparticlesfrom the solution, wherein the recovered nanoparticles have the meanparticle size of less than about 25 nanometers.
 8. The process of claim7 further comprising, after said removing at least 50% of the firstsolvent, adding a coupling agent to the solution to facilitate reactingof the coupling agent with the nanoparticles.
 9. The process of claim 2wherein the coupling agent comprises one or both of an alkoxy silanecompound and a chlorosilane compound.
 10. The process of claim 2 whereinthe coupling agent is trimethyl chlorosilane.
 11. The process of claim 2wherein the coupling agent has the formula:(RO)₃—Si—R_(T) where R is an alkyl and R_(T) is a functional group. 12.The process of claim 2 wherein the coupling agent has an end groupfunctionality that can participate in hydrolysis and condensationreaction with silanol groups of PMMSQ nanoparticles.
 13. The process ofclaim 2 wherein the coupling agent comprises one or more compoundsselected from the group consisting of aminopropyl triethoxy silane,mercaptopropyl triethoxy silane, and perfluoro alkyl dimethylchlorosilane.
 14. The process of claim 1 wherein the first solvent has aboiling point below 160 C.
 15. The process of claim 1 wherein the secondsolvent has a boiling point above 160 C.
 16. The process of claim 1wherein the first solvent is selected from alcohols, ketones, amides,esters, or combinations thereof.
 17. The process of claim 1 wherein thefirst solvent is selected from the group consisting of propylene glycolpropyl ether (PGPE), 3-heptanol, 2-methyl-1-pentanol,5-methyl-2-hexanol, 3-hexanol, 2-heptano, 2-hexanol,2,3-dimethyl-3-pentanol, propylene glycol methyl ether acetate (PGMEA),ethylene glycol n-butyl ether, propylene glycol n-butyl ether (PGBE),1-butoxy-2-propanol, 2-methyl-3-pentanol, 2-methoxyethyl acetate,2-butoxyethanol, 2-ethoxyethyl acetoacetate, 1-pentanol, and propyleneglycol methyl ether.
 18. The process of claim 1 wherein the firstsolvent is selected from the group consisting of ethanol,1-methoxy-2-propanol (propylene glycol monomethyl ether),tetrahydrofuran, acetone, 1,4-dioxane, 1,3-dioxolane, ethyl acetate, andmethyl ethyl ketone.
 19. The process of claim 1 wherein the secondsolvent is selected from the group consisting of dimethylformamide,dimethylacetamide, N-methyl pyrrolidone, ethylene carbonate, propylenecarbonate, glycerol and derivatives, naphthalene and substitutedversions, acetic acid anyhydride, propionic acid and propionic acidanhydride, dimethyl sulfone, benzophenone, diphenyl sulfone, phenol,m-cresol, dimethyl sulfoxide, diphenyl ether, and terphenyl.
 20. Theprocess of claim 1 comprising: forming the solution ofpolymethylsilsesquioxane (PMSSQ) as the organosilica nanoparticleprecursor in the mixed solvent system comprising propylene glycol methylether acetate (PGMEA) as the first solvent and poly(propylene glycol)(PPG) as the second solvent, wherein the nanoparticle precursor has agreater solubility in the PGMEA than in the PPG; removing at least 50%of the first solvent to form nanoparticles dispersed in the solution;adding trimethyl chlorosilane as the coupling agent to the solution tofacilitate reacting of the coupling agent with the nanoparticles; andrecovering the nanoparticles from the solution, wherein the recoverednanoparticles have the mean particle size of less than about 25nanometers.
 21. The process of claim 20 wherein the solution is preparedby mixing a first solution containing the PMSSQ in PGMEA with a secondsolution containing the PPG in PGMEA.
 23. The process of claim 1 whereinthe first solvent is ethanol.
 23. The process of claim 1 comprising:forming the solution of polymethylsilsesquioxane (PMSSQ) as theorganosilica nanoparticle precursor in the mixed solvent system whereinthe first solvent is ethanol; removing at least 50% of the first solventto form nanoparticles dispersed in the solution; adding trimethylchlorosilane as the coupling agent to the solution to facilitatereacting of the coupling agent with the nanoparticles; and recoveringthe nanoparticles from the solution, wherein the recovered nanoparticleshave the mean particle size of less than about 25 nanometers.
 24. Themethod of claim 1 wherein the poly(propylene glycol) (PPG) is the secondsolvent.
 25. The process of claim 1 comprising: forming the solution ofthe organosilica nanoparticle precursor in the mixed solvent systemcomprising polyethylene glycol (PEG) as the second solvent, wherein thenanoparticle precursor has a greater solubility in the first solventthan in the PEG; removing at least 50% of the first solvent to form thenanoparticles having the mean particle size less than about 25nanometers dispersed in the solution; adding the coupling agent to thesolution to facilitate reacting of the coupling agent with thenanoparticles; and recovering the nanoparticles from the solution,wherein the recovered nanoparticles have the mean particle size of lessthan about 25 nanometers.
 26. Free-flowing nanoparticles formed by theprocess of claim 1.